U.S. patent number 7,497,904 [Application Number 10/811,096] was granted by the patent office on 2009-03-03 for liquid coloring suspension and colored cementitious composition.
This patent grant is currently assigned to Construction Research & Technology GmbH, L.M. Scofield Company. Invention is credited to Nancy A. Dulzer, Jeffrey L. Matrician, Martin E. Wild.
United States Patent |
7,497,904 |
Dulzer , et al. |
March 3, 2009 |
Liquid coloring suspension and colored cementitious composition
Abstract
A cementitious composition is provided that is composed of
hydraulic cement and a liquid coloring suspension. The liquid
coloring suspension which contains polycarboxylate dispersant and
pigment provides the cementitious composition with increased
dispersion of pigment particles, lowered water content, and
improved coloration over that observed in the prior art. Also, a
liquid coloring suspension for cementitious compositions is
provided which contains polycarboxylate dispersant, pigment, and
thixotropic additive. The liquid coloring suspension increases the
color of cementitious compositions, reduces the water content and
has long term stability in that it does not become increasingly
viscous over time.
Inventors: |
Dulzer; Nancy A. (Lyndhurst,
OH), Matrician; Jeffrey L. (Chesterland, OH), Wild;
Martin E. (Marietta, GA) |
Assignee: |
Construction Research &
Technology GmbH (Trostberg, DE)
L.M. Scofield Company (Los Angeles, CA)
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Family
ID: |
33098262 |
Appl.
No.: |
10/811,096 |
Filed: |
March 26, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20040231567 A1 |
Nov 25, 2004 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60458201 |
Mar 27, 2003 |
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Current U.S.
Class: |
106/712; 106/726;
106/823; 524/5; 106/727; 106/724 |
Current CPC
Class: |
C09B
67/009 (20130101); C09B 67/0067 (20130101); C09C
3/10 (20130101); C04B 40/0039 (20130101); B01F
17/005 (20130101); C09C 3/08 (20130101); C04B
24/32 (20130101); C04B 24/2647 (20130101); B01F
17/0064 (20130101); B01F 17/0057 (20130101); B01F
17/0071 (20130101); C09C 1/00 (20130101); B01F
17/0042 (20130101); C04B 28/02 (20130101); B01F
17/0028 (20130101); B01F 17/0021 (20130101); C04B
40/0039 (20130101); C04B 2103/408 (20130101); C04B
2103/44 (20130101); C04B 2103/54 (20130101); C04B
28/02 (20130101); C04B 14/06 (20130101); C04B
18/08 (20130101); C04B 2103/408 (20130101); C04B
2103/54 (20130101); C04B 40/0039 (20130101); C04B
2103/408 (20130101); C04B 2103/54 (20130101); C04B
40/0039 (20130101); C04B 24/2641 (20130101); C04B
2103/54 (20130101); C04B 40/0039 (20130101); C04B
24/267 (20130101); C04B 2103/54 (20130101); C04B
40/0039 (20130101); C04B 24/32 (20130101); C04B
2103/54 (20130101); C04B 40/0039 (20130101); C04B
24/2647 (20130101); C04B 2103/54 (20130101); C01P
2006/60 (20130101); C04B 2103/44 (20130101); Y02W
30/92 (20150501); Y02W 30/91 (20150501); C04B
2103/408 (20130101); C01P 2006/80 (20130101); C01P
2006/22 (20130101); C04B 2103/44 (20130101); C04B
14/062 (20130101); C04B 14/10 (20130101); C04B
18/08 (20130101); C04B 24/36 (20130101); C04B
24/425 (20130101); C04B 2103/408 (20130101); C04B
24/2647 (20130101); C04B 24/2658 (20130101); C04B
24/32 (20130101); C04B 24/42 (20130101) |
Current International
Class: |
C04B
24/04 (20060101); C04B 24/12 (20060101); C04B
24/16 (20060101); C04B 24/24 (20060101) |
Field of
Search: |
;106/724,712,726,727,823
;524/5 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2 065 692 |
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Jul 1981 |
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GB |
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WO 97/10308 |
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Mar 1997 |
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WO |
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WO 01/40133 |
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Jun 2001 |
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WO |
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WO 02/094733 |
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Nov 2002 |
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WO |
|
Primary Examiner: Marcantoni; Paul
Attorney, Agent or Firm: Curatolo Sidoti Co., LPA Curatolo;
Joseph G. Sidoti; Salvatore A.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the filing date of U.S.
Provisional Application for Patent Ser. No. 60/458,201 filed Mar.
27, 2003.
Claims
We claim:
1. A method of making a colored cementitious composition without
increasing water demand comprising forming a mixture of hydraulic
cement and a liquid coloring suspension, said suspension
comprising; a. liquid; b. polycarboxylate dispersant; and c.
pigment.
2. The method of claim 1 wherein the liquid comprises water.
3. The method of claim 1 wherein the pigment comprises an inorganic
pigment.
4. The method of claim 3 wherein the inorganic pigment comprises a
metal containing pigment that comprises at least one of iron oxide,
chromium oxide, aluminum oxide, lead chromate, titanium oxide, zinc
white, zinc oxide, zinc sulfide, lead white, iron manganese black,
cobalt green, manganese blue, manganese violet, cadmium
sulfoselenide, chromium orange, nickel titanium yellow, chromium
titanium yellow, cadmium sulfide, zinc yellow, cobalt blue,
ultramarine blue or mixtures thereof.
5. The method of claim 1 wherein the pigment comprises an organic
pigment.
6. The method of claim 5 wherein the organic pigment comprises
phthalocyanine.
7. The method of claim 1, wherein the amount of polycarboxylate
dispersant solids are from about 0.5% to about 3% and, the pigment
solids are from about 50% to about 75%, based on the total weight
of the liquid coloring suspension components.
8. The method of claim 1, wherein the amount of polycarboxylate
dispersant solids are from about 1% to about 2.5%, and the pigment
solids are from about 53% to about 70%, based on the total weight
of the liquid coloring suspension components.
9. The method of claim 1, wherein the amount of polycarboxylate
dispersant solids are from about 0.0008% to about 0.51% and the
pigment solids are from about 0.1% to about 10%, by total dry
weight of cementitious binder.
10. The method of claim 1, wherein the amount of polycarboxylate
dispersant solids are from about 0.004% to about 0.25% and the
pigment solids are from about 0.25% to about 6%, by total dry
weight of cementitious binder.
11. The method of claim 1, wherein the water to cementitious
materials ratio is about 0.38 to about 0.65.
12. The method of claim 1, wherein the cement comprises at least
one of portland cement, modified portland cement, masonry cement,
or mixtures thereof.
13. The method of claim 1 further comprising a cement admixture or
additive that comprises at least one of set accelerator, set
retarder, air detraining agent, air entraining agent, foaming
agent, corrosion inhibitor, shrinkage reducing admixture, water
reducer, fiber, pozzolan, clay, strength enhancing agents, rheology
modifying agents, water repellents, wetting agents, water soluble
polymers, dampproofing admixtures, gas formers, permeability
reducers, pumping aids, fungicidal admixtures, germicidal
admixtures, insecticidal admixtures, aggregates, alkali-reaction
reducers, bonding admixtures, or mixtures thereof.
14. The method of claim 13, wherein the aggregate comprises at
least one of silica, quartz, crushed round marble, glass spheres,
granite, limestone, calcite, feldspar, alluvial sands, or sand.
15. The method of claim 13, wherein the pozzolan comprises at least
one of natural pozzolan, metakaolin, fly ash, silica fume, calcined
clay, or blast furnace slag.
16. A cementitious composition made by the method of claim 1,
wherein the liquid coloring suspension improves the color in the
cementitious composition without increasing the water demand.
17. The cementitious composition of claim 16 wherein the liquid
comprises water.
18. The cementitious composition of claim 16 wherein the pigment
comprises an inorganic pigment.
19. The cementitious composition of claim 18 wherein the inorganic
pigment comprises a metal containing pigment that comprises at
least one of iron oxide, chromium oxide, aluminum oxide, lead
chromate, titanium oxide, zinc white, zinc oxide, zinc sulfide,
lead white, iron manganese black, cobalt green, manganese blue,
manganese violet, cadmium sulfoselenide, chromium orange, nickel
titanium yellow, chromium titanium yellow, cadmium sulfide, zinc
yellow, cobalt blue, ultramarine blue or mixtures thereof.
20. The cementitious composition of claim 16 wherein the pigment
comprises an organic pigment.
21. The cementitious composition of claim 20 wherein the organic
pigment comprises phthalocyanine.
22. The cementitious composition of claim 16, wherein the amount of
polycarboxylate dispersant solids are from about 0.5% to about 3%
and, the pigment solids are from about 50% to about 75%, based on
the total weight of the liquid coloring suspension components.
23. The cementitious composition of claim 16, wherein the amount of
polycarboxylate dispersant solids are from about 1% to about 2.5%
and, the pigment solids are from about 53% to about 70%, based on
the total weight of the liquid coloring suspension components.
24. The cementitious composition of claim 16, wherein the amount of
polycarboxylate dispersant solids are from about 0.0008% to about
0.51% and the pigment solids are from about 0.1% to about 10%, by
total dry weight of cementitious binder.
25. The cementitious composition of claim 16, wherein the amount of
polycarboxylate dispersant solids are from about 0.004% to about
0.25% and the pigment solids are from about 0.25% to about 6%, by
total dry weight of cementitious binder.
26. The cementitious composition of claim 17, wherein the water to
cementitious materials ratio is about 0.38 to about 0.65.
27. The cementitious composition of claim 16, wherein the cement
comprises at least one of portland cement, modified portland
cement, masonry cement, or mixtures thereof.
28. The cementitious composition of claim 16 further comprising a
cement admixture or additive that comprises at least one of set
accelerator, set retarder, air detraining agent, air entraining
agent, foaming agent, corrosion inhibitor, shrinkage reducing
admixture, water reducer, fiber, pozzolan, strength enhancing
agents, rheology modifying agents, water repellents, wetting
agents, water soluble polymers, dampproofing admixtures, gas
formers, permeability reducers, pumping aids, fungicidal
admixtures, germicidal admixtures, insecticidal admixtures,
aggregates, alkali-reaction reducers, bonding admixtures, or
mixtures thereof.
29. The cementitious composition of claim 28, wherein the aggregate
comprises at least one of silica, quartz, crushed round marble,
glass spheres, granite, limestone, calcite, feldspar, alluvial
sands, or sand.
30. The cementitious composition of claim 28, wherein the pozzolan
comprises at least one of natural pozzolan, metakaolin, fly ash,
silica fume, calcined clay, or blast furnace slag.
31. The method of claim 1 wherein the polycarboxylate dispersant of
the liquid coloring suspension is at least one of: a) a dispersant
of Formula (I): ##STR00020## wherein in Formula (I) X is at least
one of hydrogen, an alkali earth metal ion, an alkaline earth metal
ion, ammonium ion, or amine; R is at least one of C.sub.1 to
C.sub.6 alkyl(ene) ether or mixtures thereof or C.sub.1 to C.sub.6
alkyl(ene) imine or mixtures thereof; Q is at least one of oxygen,
NH, or sulfur; p is a number from 1 to about 300 resulting in at
least one of a linear side chain or branched side chain; R.sub.1 is
at least one of hydrogen, C.sub.1 to C.sub.20 hydrocarbon, or
functionalized hydrocarbon containing at least one of --OH, --COOH,
an ester or amide derivative of --COOH, sulfonic acid, an ester or
amide derivative of sulfonic acid, amine, or epoxy; Y is at least
one of hydrogen, an alkali earth metal ion, an alkaline earth metal
ion, ammonium ion, amine, a hydrophobic hydrocarbon or polyalkylene
oxide moiety that functions as a defoamer; m, m', m'', n, n', and
n'' are each independently 0 or an integer between 1 and about 20;
Z is a moiety containing at least one of i) at least one amine and
one acid group, ii) two functional groups capable of incorporating
into the backbone selected from the group consisting of
dianhydrides, dialdehydes, and di-acid-chlorides, or iii) an imide
residue; and wherein a, b, c, and d reflect the mole fraction of
each unit wherein the sum of a, b, c, and d equal one, wherein a,
b, c, and d are each a value greater than or equal to zero and less
than one, and at least two of a, b, c, and d are greater than zero;
b) a dispersant of Formula (II): ##STR00021## wherein in Formula
(II): A is COOM or optionally in the "y" structure an acid
anhydride group (--CO--O--CO--) is formed in place of the A groups
between the carbon atoms to which the A groups are bonded to form
an anhydride; B is COOM M is hydrogen, a transition metal cation,
the residue of a hydrophobic polyalkylene glycol or polysiloxane,
an alkali metal ion, an alkaline earth metal ion, ferrous ion,
aluminum ion, (alkanol)ammonium ion, or (alkyl)ammonium ion; R is a
C.sub.2-6 alkylene radical; R1 is a C.sub.1-20 alkyl, C.sub.6-9
cycloalkyl, or phenyl group; x, y, and z are a number from 0.01 to
100; m is a number from 1 to 100; and n is a number from 10 to 100;
c) a dispersant comprising at least one polymer or a salt thereof
having the form of a copolymer of i) a maleic anhydride half-ester
with a compound of the formula RO(AO).sub.mH, wherein R is a
C.sub.1-C.sub.20 alkyl group, A is a C.sub.2-4 alkylene group, and
m is an integer from 2-16; and ii) a monomer having the formula
CH.sub.2.dbd.CHCH.sub.2--(OA).sub.nOR, wherein n is an integer from
1-90 and R is a C.sub.1-20 alkyl group; d) a dispersant obtained by
copolymerizing 5 to 98% by weight of an (alkoxy)polyalkylene glycol
mono(meth)acrylic ester monomer (a) represented by the following
general formula (1): ##STR00022## wherein R.sub.1 stands for
hydrogen atom or a methyl group, R.sub.2O for one species or a
mixture of two or more species of oxyalkylene group of 2 to 4
carbon atoms, providing two or more species of the mixture may be
added either in the form of a block or in a random form, R.sub.3
for a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m
is a value indicating the average addition mol number of
oxyalkylene groups that is an integer in the range of 1 to 100, 95
to 2% by weight of a (meth)acrylic acid monomer (b) represented by
the above general formula (2), wherein R.sub.4 and R.sub.5 are each
independently a hydrogen atom or a methyl group, and M.sub.1 for a
hydrogen atom, a monovalent metal atom, a divalent metal atom, an
ammonium group, or an organic amine group, and 0 to 50% by weight
of other monomer (c) copolymerizable with these monomers, provided
that the total amount of (a), (b), and (c) is 100% by weight; e) a
graft polymer that is a polycarboxylic acid or a salt thereof,
having side chains derived from at least one species selected from
the group consisting of oligoalkyleneglycols, polyalcohols,
polyoxyalkylene amines, and polyalkylene glycols; f) a dispersant
of Formula (III): ##STR00023## wherein in Formula (III): D=a
component selected from the group consisting of the structure d1,
the structure d2, and mixtures thereof; X.dbd.H, CH.sub.3, C.sub.2
to C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl;
Y=H or --COOM; R=H or CH.sub.3; Z=H, --SO.sub.3M, --PO.sub.3M,
--COOM, --O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3,
or --(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, --CONHR.sub.3,
--CONHC(CH.sub.3).sub.2CH.sub.2SO.sub.3M, --COO(CHR.sub.4).sub.nOH
where n=2 to 6, or --O(CH.sub.2).sub.nOR.sub.4 wherein n=2 to 6;
R.sub.1, R.sub.2, R.sub.3, R.sub.5 are each independently
--(CHRCH.sub.2O).sub.mR.sub.4 random copolymer of oxyethylene units
and oxypropylene units where m=10 to 500 and wherein the amount of
oxyethylene in the random copolymer is from about 60% to 100% and
the amount of oxypropylene in the random copolymer is from 0% to
about 40%; R.sub.4=H, Methyl, C.sub.2 to about C.sub.6 Alkyl, or
about C.sub.6 to about C.sub.10 aryl; M=H, Alkali Metal, Alkaline
Earth Metal, Ammonium, Amine, triethanol amine, Methyl, or C.sub.2
to about C.sub.6 Alkyl; a=0 to about 0.8; b=about 0.2 to about 1.0;
c=0 to about 0.5; d=0 to about 0.5; and wherein a, b, c, and d
represent the mole fraction of each unit and the sum of a, b, c,
and d is 1.0; g) a dispersant of Formula (IV): ##STR00024## wherein
in Formula (IV): the "b" structure is one of a carboxylic acid
monomer, an ethylenically unsaturated monomer, or maleic anhydride
wherein an acid anhydride group (--CO--O--CO--) is formed in place
of the groups Y and Z between the carbon atoms to which the groups
Y and Z are bonded respectively, and the "b" structure must include
at least one moiety with a pendant ester linkage and at least one
moiety with a pendant amide linkage; X=H, CH.sub.3, C.sub.2 to
C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, p-Ethyl Phenyl,
Carboxylated Phenyl, or Sulfonated Phenyl; Y=H, --COOM, --COOH, or
W; W=a hydrophobic defoamer represented by the formula
R.sub.5O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2C(CH.sub.3)HO).sub.t--(CH.s-
ub.2CH.sub.2O).sub.u where s, t, and u are integers from 0 to 200
with the proviso that t>(s+u) and wherein the total amount of
hydrophobic defoamer is present in an amount less than about 10% by
weight of the polycarboxylate dispersant; Z=H, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3,
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, or --CONHR.sub.3;
R.sub.1=H, or CH.sub.3; R.sub.2, R.sub.3, are each independently a
random copolymer of oxyethylene units and oxypropylene units of the
general formula --(CH(R.sub.1)CH.sub.2O).sub.mR.sub.4 where m=10 to
500 and wherein the amount of oxyethylene in the random copolymer
is from about 60% to 100% and the amount of oxypropylene in the
random copolymer is from 0% to about 40%; R.sub.4=H, Methyl, or
C.sub.2 to C.sub.8 Alkyl; R.sub.5=C.sub.1 to C.sub.18 alkyl or
C.sub.6 to C.sub.18 alkyl aryl; M=Alkali Metal, Alkaline Earth
Metal, Ammonia, Amine, monoethanol amine, diethanol amine,
triethanol amine, morpholine, imidazole; a=0.01-0.8; b=0.2-0.99;
c=0-0.5; and wherein a, b, c represent the mole fraction of each
unit and the sum of a, b, and c, is 1; h) a random copolymer
corresponding to the following Formula (V) in free acid or salt
form having the following monomer units and numbers of monomer
units: ##STR00025## wherein A is selected from the moieties (i) or
(ii) ##STR00026## (i) --CR.sub.1R.sub.2--CR.sub.3R.sub.4-- wherein
R.sub.1 and R.sub.3 are selected from substituted benzene,
C.sub.1-8 alkyl, C.sub.2-8 alkenyl, C.sub.2-8 alkylcarbonyl,
C.sub.1-8 alkoxy, carboxyl, hydrogen, and a ring, R.sub.2 and
R.sub.4 are selected from the group consisting of hydrogen and
C.sub.1-4 alkyl, wherein R.sub.1 and R.sub.3 can together with
R.sub.2 and/or R.sub.4 when R.sub.2 and/or R.sub.4 are C.sub.1-4
alkyl form the ring; R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are
individually selected from the group consisting of hydrogen,
C.sub.1-6 alkyl, and a C.sub.2-8 hydrocarbon chain, wherein R.sub.1
and R.sub.3 together with R.sub.7 and/or R.sub.8, R.sub.9, and
R.sub.10 form the C.sub.2-8 hydrocarbon chain joining the carbon
atoms to which they are attached, the hydrocarbon chain optionally
having at least one anionic group, wherein the at least one anionic
group is optionally sulfonic; M is selected from the group
consisting of hydrogen, and the residue of a hydrophobic
polyalkylene glycol or a polysiloxane, with the proviso that when A
is (ii) and M is the residue of a hydrophobic polyalkylene glycol,
M must be different from the group --(R.sub.5O).sub.mR.sub.6;
R.sub.5 is a C.sub.2-8 alkylene radical; R.sub.6 is selected from
the group consisting of C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl and
phenyl; n, x, and z are numbers from 1 to 100; y is 0 to 100; m is
2 to 1000; the ratio of x to (y+z) is from 1:10 to 10:1 and the
ratio of y:z is from 5:1 to 1:100; i) a copolymer of
oxyalkyleneglycol-alkenyl ethers and unsaturated dicarboxylic
acids, comprising: i) 0 to 90 mol % of at least one component of
the formula 3a or 3b: ##STR00027## wherein M is a hydrogen atom, a
mono- or divalent metal cation, an ammonium ion or an organic amine
residue, a is 1, or when M is a divalent metal cation a is 1/2;
wherein X is --OM.sub.a, --O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in
which R.sup.1 is a hydrogen atom, an aliphatic hydrocarbon radical
containing from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon
radical containing 5 to 8 carbon atoms or an optionally hydroxyl,
carboxyl, C.sub.1-14 alkyl, or sulphonic substituted aryl radical
containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; ii) 1 to 89 mol % of components of the general
formula 4: ##STR00028## wherein R.sub.3 is a hydrogen atom or an
aliphatic hydrocarbon radical containing from 1 to 5 carbon atoms,
p is 0 to 3, and R.sub.1 is hydrogen, an aliphatic hydrocarbon
radical containing from 1 to 20 carbon atoms, a cycloaliphatic
hydrocarbon radical containing 5 to 8 carbon atoms or an optionally
hydroxyl, carboxyl, C.sub.1-14 alkyl, or sulfonic substituted aryl
radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to
100, and iii) 0.1 to 10 mol % of at least one component of the
formula 5a or 5b: ##STR00029## wherein S is a hydrogen atom or
--COOM.sub.a or --COOR.sub.5, T is --COOR.sub.5, --W--R.sub.7,
--CO--[--NH--(CH2)3)--].sub.s--W--R.sub.7,
--CO--O--(CH.sub.2).sub.z--W--R.sub.7, a radical of the general
formula: ##STR00030## or
--(CH.sub.2).sub.z--V--(CH.sub.2).sub.z--CH.dbd.CH--R.sub.1, or
when S is --COOR.sub.5 or --COOM.sub.a, U.sub.1 is --CO--NHM--,
--O-- or --CH.sub.2O, U.sub.2 is --NH--CO--, --O-- or --OCH.sub.2,
V is --O--CO--C.sub.6H.sub.4--CO--O-- or --W--, and W is
##STR00031## R4 is a hydrogen atom or a methyl radical, R5 is an
aliphatic hydrocarbon radical containing 3 to 20 carbon atoms, a
cycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms
or an aryl radical containing 6 to 14 carbon atoms,
R.sub.6.dbd.R.sub.1 or ##STR00032## r is 2 to 100, s is 1 or 2, x
is 1 to 150, y is 0 to 15 and z is 0 to 4; iv) 0 to 90 mol % of at
least one component of the formula 6a, 6b, or 6c: ##STR00033##
wherein M is a hydrogen atom, a mono- or divalent metal cation, an
ammonium ion or an organic amine residue, a is 1, or when M is a
divalent metal cation a is 1/2; wherein X is --OM.sub.a,
--O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in which R.sup.1 is a
hydrogen atom, an aliphatic hydrocarbon radical containing from 1
to 20 carbon atoms, a cycloaliphatic hydrocarbon radical containing
5 to 8 carbon atoms or an optionally hydroxyl, carboxyl, C.sub.1-14
alkyl, or sulphonic substituted aryl radical containing 6 to 14
carbon atoms, m is 2 to 4, and n is 0 to 100,
--NH--(C.sub.mH.sub.2mO).sub.n----R.sup.1,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; j) a copolymer of dicarboxylic acid derivatives
and oxyalkylene glycol-alkenyl ethers, comprising: i) 1 to 90 mol.
% of at least one member selected from the group consisting of
structural units of formula 7a and formula 7b: ##STR00034## wherein
M is H, a monovalent metal cation, a divalent metal cation, an
ammonium ion or an organic amine; a is 1/2 when M is a divalent
metal cation or 1 when M is a monovalent metal cation; wherein
R.sup.1 is --OM.sub.a, or --O--(C.sub.mH.sub.2mO).sub.n--R.sup.2
wherein R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; ii) 0.5 to 80
mol. % of the structural units of formula 8: ##STR00035## wherein
R.sup.3 is H or a C.sub.1-5 aliphatic hydrocarbon; p is 0 to 3;
R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; iii) 0.5 to 80
mol. % structural units selected from the group consisting of
formula 9a and formula 9b: ##STR00036## wherein R.sup.4 is H,
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one hydroxyl group,
--(C.sub.mH.sub.2mO).sub.n--R.sup.2, --CO--NH--R.sup.2, C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; M is H, a monovalent metal cation, a divalent
metal cation, an ammonium ion or an organic amine; a is 1/2 when M
is a divalent metal cation or 1 when M is a monovalent metal
cation; R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; iv) 1 to 90 mol.
% of structural units of formula 10 ##STR00037## wherein R.sup.5 is
methyl, or methylene group, wherein R.sup.5 forms one or more 5 to
8 membered rings with R.sup.7; R.sup.6 is H, methyl, or ethyl;
R.sup.7 is H, a C.sub.1-20 aliphatic hydrocarbon, a C.sub.6-14 aryl
that is optionally substituted with at least one member selected
from the group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2, a C.sub.5-8 cycloaliphatic hydrocarbon,
--OCOR.sup.4, --OR.sup.4, and --COOR.sup.4, wherein R.sup.4 is H, a
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one --OH, --(C.sub.mH.sub.2mO).sub.n--R.sup.2,
--CO--NH--R.sup.2, C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl residue that is optionally substituted with a
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2.
32. A cementitious composition made by the method of claim 31.
33. The cementitious composition of claim 32 wherein the liquid
comprises water.
34. The cementitious composition of claim 32 wherein the pigment
comprises an inorganic pigment.
35. The cementitious composition of claim 34 wherein the inorganic
pigment comprises a metal containing pigment that comprises at
least one of iron oxide, chromium oxide, aluminum oxide, lead
chromate, titanium oxide, zinc white, zinc oxide, zinc sulfide,
lead white, iron manganese black, cobalt green, manganese blue,
manganese violet, cadmium sulfoselenide, chromium orange, nickel
titanium yellow, chromium titanium yellow, cadmium sulfide, zinc
yellow, cobalt blue, ultramarine blue or mixtures thereof.
36. The cementitious composition of claim 32 wherein the pigment
comprises an organic pigment.
37. The cementitious composition of claim 36 wherein the organic
pigment comprises phthalocyanine.
38. The cementitious composition of claim 32, wherein the amount of
polycarboxylate dispersant solids are from about 0.5% to about 3%
and, the pigment solids are from about 50% to about 75%, based on
the total weight of the liquid coloring suspension components.
39. The cementitious composition of claim 32, wherein the amount of
polycarboxylate dispersant solids are from about 1% to about 2.5%
and, the pigment solids are from about 53% to about 70%, based on
the total weight of the liquid coloring suspension components.
40. The cementitious composition of claim 32, wherein the amount of
polycarboxylate dispersant solids are from about 0.0008% to about
0.51% and the pigment solids are from about 0.1% to about 10%, by
total dry weight of cementitious binder.
41. The cementitious composition of claim 32, wherein the amount of
polycarboxylate dispersant solids are from about 0.004% to about
0.25% and the pigment solids are from about 0.25% to about 6%, by
total dry weight of cementitious binder.
42. The cementitious composition of claim 33, wherein the water to
cementitious materials ratio is about 0.38 to about 0.65.
43. The cementitious composition of claim 32, wherein the cement is
at least one of portland cement, modified portland cement, masonry
cement, or mixtures thereof.
44. The cementitious composition of claim 32 further comprising a
cement admixture or additive that comprises at least one of set
accelerator, set retarder, air detraining agent, air entraining
agent, foaming agent, corrosion inhibitor, shrinkage reducing
admixture, water reducer, fiber, pozzolan, strength enhancing
agents, rheology modifying agents, water repellents, wetting
agents, water soluble polymers, dampproofing admixtures, gas
formers, permeability reducers, pumping aids, fungicidal
admixtures, germicidal admixtures, insecticidal admixtures,
aggregates, alkali-reaction reducers, bonding admixtures, or
mixtures thereof.
45. The cementitious composition of claim 44, wherein the aggregate
comprises at least one of silica, quartz, crushed round marble,
glass spheres, granite, limestone, calcite, feldspar, alluvial
sands, or sand.
46. The cementitious composition of claim 44, wherein the pozzolan
comprises at least one of natural pozzolan, metakaolin, fly ash,
silica fume, calcined clay, or blast furnace slag.
47. A liquid coloring suspension comprising: a. liquid b.
polycarboxylate dispersant; c. pigment; and d. thixotropic
additive; wherein the viscosity of the liquid coloring suspension
is stable over time.
48. The liquid coloring suspension of claim 47, wherein the amount
of polycarboxylate dispersant solids are from about 0.5% to about
3%, pigment solids are from about 50% to about 75%, and thixotropic
additive is from about 0.05% to about 1%, based on the total weight
of the liquid coloring suspension.
49. The liquid coloring suspension of claim 47, wherein the amount
of polycarboxylate dispersant solids are from about 1% to about
2.5%, pigment solids are from about 53% to about 70%, and
thixotropic additive is from about 0.1% to about 0.7%, based on the
total weight of the liquid coloring suspension.
50. The liquid coloring suspension of claim 47 wherein the liquid
comprises water.
51. The liquid coloring suspension of claim 47 wherein the pigment
comprises an inorganic pigment.
52. The liquid coloring suspension of claim 51 wherein the
inorganic pigment comprises a metal containing pigment that
comprises at least one of iron oxide, chromium oxide, aluminum
oxide, lead chromate, titanium oxide, zinc white, zinc oxide, zinc
sulfide, lead white, iron manganese black, cobalt green, manganese
blue, manganese violet, cadmium sulfoselenide, chromium orange,
nickel titanium yellow, chromium titanium yellow, cadmium sulfide,
zinc yellow, cobalt blue, ultramarine blue or mixtures thereof.
53. The liquid coloring suspension of claim 47 wherein the pigment
comprises an organic pigment.
54. The liquid coloring suspension of claim 53 wherein the organic
pigment comprises phthalocyanine.
55. The liquid coloring suspension of claim 47 wherein the
thixotropic additive comprises at least one of organic flocculents,
organic emulsions of paraffin, coal tar, asphalt, acrylics,
bentonite, pyrogenic silicas, natural pozzolans, fly ash, hydrated
lime, organoclay, cellulose or mixtures thereof.
56. The liquid coloring suspension of claim 55 wherein the
organoclay comprises at least one of hectorite clay or smectite
clay.
57. The liquid coloring suspension of claim 47 further comprising
at least one of set accelerators, set retarders, air detraining
agents, air entraining agents, shrinkage reducing admixtures, water
reducers, foaming agents, dampproofing admixtures, pumping aids,
fungicidal admixtures, insecticidal admixtures, germicidal
admixtures, alkali activity reducers, bonding admixtures, or
corrosion inhibitors.
58. A colored cementitious composition comprising hydraulic cement
and a liquid coloring suspension, said liquid coloring suspension
comprising: a. liquid; b. polycarboxylate dispersant; c. pigment;
and d. thixotropic additive; wherein the liquid coloring suspension
improves the color in the cementitious composition without
increasing the water demand.
59. The colored cementitious composition of claim 58 wherein the
liquid comprises water.
60. The colored cementitious composition of claim 58 wherein the
pigment comprises an inorganic pigment.
61. The colored cementitious composition of claim 60 wherein the
inorganic pigment comprises a metal containing pigment that
comprises at least one of iron oxide, chromium oxide, aluminum
oxide, lead chromate, titanium oxide, zinc white, zinc oxide, zinc
sulfide, lead white, iron manganese black, cobalt green, manganese
blue, manganese violet, cadmium sulfoselenide, chromium orange,
nickel titanium yellow, chromium titanium yellow, cadmium sulfide,
zinc yellow, cobalt blue, ultramarine blue or mixtures thereof.
62. The colored cementitious composition of claim 58 wherein the
pigment comprises an organic pigment.
63. The colored cementitious composition of claim 62 wherein the
organic pigment comprises phthalocyanine.
64. The colored cementitious composition of claim 58 wherein the
thixotropic additive comprises at least one of organic flocculents,
organic emulsions of paraffin, coal tar, asphalt, acrylics,
bentonite, pyrogenic silicas, natural pozzolans, fly ash, hydrated
lime, organoclay, cellulose or mixtures thereof.
65. The colored cementitious composition of claim 64 wherein the
organoclay comprises at least one of hectorite clay or smectite
clay.
66. The colored cementitious composition of claim 58, wherein the
amount of polycarboxylate dispersant solids are from about 0.0008%
to about 0.51%, pigment solids are from about 0.1% to about 10%,
and thixotropic additive is from about 0.00008% to about 0.17%, by
total dry weight of cementitious binder.
67. The colored cementitious composition of claim 58, wherein the
amount of polycarboxylate dispersant solids are from about 0.004%
to about 0.25%, pigment solids are from about 0.25% to about 6%,
and thixotropic additive is from about 0.0004% to about 0.07%, by
total dry weight of cementitious binder.
68. The cementitious composition of claim 59, wherein the water to
cementitious composition ratio is about 0.38 to about 0.65.
69. The colored cementitious composition of claim 58, wherein the
cement comprises at least one of portland cement, modified portland
cement, masonry cement, or mixtures thereof.
70. The colored cementitious composition of claim 58 further
comprising a cement admixture or additive that comprises at least
one of set accelerator, set retarder, air detraining agent, air
entraining agent, foaming agent, corrosion inhibitor, shrinkage
reducing admixture, water reducer, fiber, pozzolan, strength
enhancing agents, rheology modifying agents, water repellents,
wetting agents, water soluble polymers, dampproofing admixtures,
gas formers, permeability reducers, pumping aids, fungicidal
admixtures, germicidal admixtures, insecticidal admixtures,
aggregates, alkali-reaction reducers, bonding admixtures, or
mixtures thereof.
71. The colored cementitious composition of claim 70, wherein the
aggregate comprises at least one of silica, quartz, crushed round
marble, glass spheres, granite, limestone, calcite, feldspar,
alluvial sands, or sand.
72. The colored cementitious composition of claim 70, wherein the
pozzolan comprises at least one of natural pozzolan, metakaolin,
fly ash, silica fume, calcined clay, or blast furnace slag.
73. The colored cementitious composition of claim 58 wherein the
polycarboxylate dispersant of the liquid coloring suspension is at
least one of: a) a dispersant of Formula (I): ##STR00038## wherein
in Formula (I) X is at least one of hydrogen, an alkali earth metal
ion, an alkaline earth metal ion, ammonium ion, or amine; R is at
least one of C.sub.1 to C.sub.6 alkyl(ene) ether or mixtures
thereof or C.sub.1 to C.sub.6 alkyl(ene) imine or mixtures thereof;
Q is at least one of oxygen, NH, or sulfur; p is a number from 1 to
about 300 resulting in at least one of a linear side chain or
branched side chain; R.sub.1 is at least one of hydrogen, C.sub.1
to C.sub.20 hydrocarbon, or functionalized hydrocarbon containing
at least one of --OH, --COOH, an ester or amide derivative of
--COOH, sulfonic acid, an ester or amide derivative of sulfonic
acid, amine, or epoxy; Y is at least one of hydrogen, an alkali
earth metal ion, an alkaline earth metal ion, ammonium ion, amine,
a hydrophobic hydrocarbon or polyalkylene oxide moiety that
functions as a defoamer; m, m', m'', n, n', and n'' are each
independently 0 or an integer between 1 and about 20; Z is a moiety
containing at least one of i) at least one amine and one acid
group, ii) two functional groups capable of incorporating into the
backbone selected from the group consisting of dianhydrides,
dialdehydes, and di-acid-chlorides, or iii) an imide residue; and
wherein a, b, c, and d reflect the mole fraction of each unit
wherein the sum of a, b, c, and d equal one, wherein a, b, c, and d
are each a value greater than or equal to zero and less than one,
and at least two of a, b, c, and d are greater than zero; b) a
dispersant of Formula (II): ##STR00039## wherein in Formula (II): A
is COOM or optionally in the "y" structure an acid anhydride group
(--CO--O--CO--) is formed in place of the A groups between the
carbon atoms to which the A groups are bonded to form an anhydride;
B is COOM M is hydrogen, a transition metal cation, the residue of
a hydrophobic polyalkylene glycol or polysiloxane, an alkali metal
ion, an alkaline earth metal ion, ferrous ion, aluminum ion,
(alkanol)ammonium ion, or (alkyl)ammonium ion; R is a C.sub.2-6
alkylene radical; R1 is a C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl,
or phenyl group; x, y, and z are a number from 0.01 to 100; m is a
number from 1 to 100; and n is a number from 10 to 100; c) a
dispersant comprising at least one polymer or a salt thereof having
the form of a copolymer of i) a maleic anhydride half-ester with a
compound of the formula RO(AO).sub.mH, wherein R is a
C.sub.1-C.sub.20 alkyl group, A is a C.sub.2-4 alkylene group, and
m is an integer from 2-16; and ii) a monomer having the formula
CH.sub.2.dbd.CHCH.sub.2--(OA).sub.nOR, wherein n is an integer from
1-90 and R is a C.sub.1-20 alkyl group; d) a dispersant obtained by
copolymerizing 5 to 98% by weight of an (alkoxy)polyalkylene glycol
mono(meth)acrylic ester monomer (a) represented by the following
general formula (1): ##STR00040## wherein R.sub.1 stands for
hydrogen atom or a methyl group, R.sub.2O for one species or a
mixture of two or more species of oxyalkylene group of 2 to 4
carbon atoms, providing two or more species of the mixture may be
added either in the form of a block or in a random form, R.sub.3
for a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m
is a value indicating the average addition mol number of
oxyalkylene groups that is an integer in the range of 1 to 100, 95
to 2% by weight of a (meth)acrylic acid monomer (b) represented by
the above general formula (2), wherein R.sub.4 and R.sub.5 are each
independently a hydrogen atom or a methyl group, and M.sub.1 for a
hydrogen atom, a monovalent metal atom, a divalent metal atom, an
ammonium group, or an organic amine group, and 0 to 50% by weight
of other monomer (c) copolymerizable with these monomers, provided
that the total amount of (a), (b), and (c) is 100% by weight; e) a
graft polymer that is a polycarboxylic acid or a salt thereof,
having side chains derived from at least one species selected from
the group consisting of oligoalkyleneglycols, polyalcohols,
polyoxyalkylene amines, and polyalkylene glycols; f) a dispersant
of Formula (III): ##STR00041## wherein in Formula (III): D=a
component selected from the group consisting of the structure d1,
the structure d2, and mixtures thereof; X=H, CH.sub.3, C.sub.2 to
C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl; Y=H
or --COOM; R=H or CH.sub.3; Z=H, --SO.sub.3M, --PO.sub.3M, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3, or
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, --CONHR.sub.3,
--CONHC(CH.sub.3).sub.2CH.sub.2SO.sub.3M, --COO(CHR.sub.4).sub.nOH
where n=2 to 6, or --(CH.sub.2).sub.nOR.sub.4 wherein n=2 to 6;
R.sub.1, R.sub.2, R.sub.3, R.sub.5 are each independently
--(CHRCH.sub.2O).sub.mR.sub.4 random copolymer of oxyethylene units
and oxypropylene units where m=10 to 500 and wherein the amount of
oxyethylene in the random copolymer is from about 60% to 100% and
the amount of oxypropylene in the random copolymer is from 0% to
about 40%; R.sub.4.dbd.H, Methyl, C.sub.2 to about C.sub.6 Alkyl,
or about C.sub.6 to about C.sub.10 aryl; M=H, Alkali Metal,
Alkaline Earth Metal, Ammonium, Amine, triethanol amine, Methyl, or
C.sub.2 to about C.sub.6 Alkyl; a=0 to about 0.8; b=about 0.2 to
about 1.0; c=0 to about 0.5; d=0 to about 0.5; and wherein a, b, c,
and d represent the mole fraction of each unit and the sum of a, b,
c, and d is 1.0; g) a dispersant of Formula (IV): ##STR00042##
wherein in Formula (IV): the "b" structure is one of a carboxylic
acid monomer, an ethylenically unsaturated monomer, or maleic
anhydride wherein an acid anhydride group (--CO--O--CO--) is formed
in place of the groups Y and Z between the carbon atoms to which
the groups Y and Z are bonded respectively, and the "b" structure
must include at least one moiety with a pendant ester linkage and
at least one moiety with a pendant amide linkage; X=H, CH.sub.3,
C.sub.2 to C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, p-Ethyl Phenyl,
Carboxylated Phenyl, or Sulfonated Phenyl; Y=H, --COOM, --COOH, or
W; W=a hydrophobic defoamer represented by the formula
R.sub.5O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2C(CH.sub.3)HO).sub.t--(CH.s-
ub.2CH.sub.2O).sub.u where s, t, and u are integers from 0 to 200
with the proviso that t>(s+u) and wherein the total amount of
hydrophobic defoamer is present in an amount less than about 10% by
weight of the polycarboxylate dispersant; Z=H, --COOM,
--(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3,
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, or --CONHR.sub.3;
R.sub.1=H, or CH.sub.3; R.sub.2, R.sub.3, are each independently a
random copolymer of oxyethylene units and oxypropylene units of the
general formula --(CH(R.sub.1)CH.sub.2O).sub.mR.sub.4 where m=10 to
500 and wherein the amount of oxyethylene in the random copolymer
is from about 60% to 100% and the amount of oxypropylene in the
random copolymer is from 0% to about 40%; R.sub.4=H, Methyl, or
C.sub.2 to C.sub.8 Alkyl; R.sub.5=C.sub.1 to C.sub.18 alkyl or
C.sub.6 to C.sub.18 alkyl aryl; M=Alkali Metal, Alkaline Earth
Metal, Ammonia, Amine, monoethanol amine, diethanol amine,
triethanol amine, morpholine, imidazole; a=0.01-0.8; b=0.2-0.99;
c=0-0.5; and wherein a, b, c represent the mole fraction of each
unit and the sum of a, b, and c, is 1; h) a random copolymer
corresponding to the following Formula (V) in free acid or salt
form having the following monomer units and numbers of monomer
units: ##STR00043## wherein A is selected from the moieties (i) or
(ii) ##STR00044## (i) --CR.sub.1R.sub.2--CR.sub.3R.sub.4-- wherein
R.sub.1 and R.sub.3 are selected from substituted benzene,
C.sub.1-8 alkyl, C.sub.2-8 alkenyl, C.sub.2-8 alkylcarbonyl,
C.sub.1-8 alkoxy, carboxyl, hydrogen, and a ring, R.sub.2 and
R.sub.4 are selected from the group consisting of hydrogen and
C.sub.1-4 alkyl, wherein R.sub.1 and R.sub.3 can together with
R.sub.2 and/or R.sub.4 when R.sub.2 and/or R.sub.4 are C.sub.1-4
alkyl form the ring; R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are
individually selected from the group consisting of hydrogen,
C.sub.1-6 alkyl, and a C.sub.2-8 hydrocarbon chain, wherein R.sub.1
and R.sub.3 together with R.sub.7 and/or R.sub.8, R.sub.9, and
R.sub.10 form the C.sub.2-8 hydrocarbon chain joining the carbon
atoms to which they are attached, the hydrocarbon chain optionally
having at least one anionic group, wherein the at least one anionic
group is optionally sulfonic; M is selected from the group
consisting of hydrogen, and the residue of a hydrophobic
polyalkylene glycol or a polysiloxane, with the proviso that when A
is (ii) and M is the residue of a hydrophobic polyalkylene glycol,
M must be different from the group --(R.sub.5O).sub.mR.sub.6;
R.sub.5 is a C.sub.2-8 alkylene radical; R.sub.6 is selected from
the group consisting of C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl and
phenyl; n, x, and z are numbers from 1 to 100; y is 0 to 100; m is
2 to 1000; the ratio of x to (y+z) is from 1:10 to 10:1 and the
ratio of y:z is from 5:1 to 1:100; i) a copolymer of
oxyalkyleneglycol-alkenyl ethers and unsaturated dicarboxylic
acids, comprising: i) 0 to 90 mol % of at least one component of
the formula 3a or 3b: ##STR00045## wherein M is a hydrogen atom, a
mono- or divalent metal cation, an ammonium ion or an organic amine
residue, a is 1, or when M is a divalent metal cation a is 1/2;
wherein X is --OM.sub.a, --O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in
which R.sup.1 is a hydrogen atom, an aliphatic hydrocarbon radical
containing from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon
radical containing 5 to 8 carbon atoms or an optionally hydroxyl,
carboxyl, C.sub.1-14 alkyl, or sulphonic substituted aryl radical
containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; ii) 1 to 89 mol % of components of the general
formula 4: ##STR00046## wherein R.sub.3 is a hydrogen atom or an
aliphatic hydrocarbon radical containing from 1 to 5 carbon atoms,
p is 0 to 3, and R.sub.1 is hydrogen, an aliphatic hydrocarbon
radical containing from 1 to 20 carbon atoms, a cycloaliphatic
hydrocarbon radical containing 5 to 8 carbon atoms or an optionally
hydroxyl, carboxyl, C.sub.1-14 alkyl, or sulfonic substituted aryl
radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to
100, and iii) 0.1 to 10 mol % of at least one component of the
formula 5a or 5b: ##STR00047## wherein S is a hydrogen atom or
--COOM.sub.a or --COOR.sub.5, T is --COOR.sub.5, --W--R.sub.7,
--CO--[--NH--(CH2)3)-].sub.5-W--R.sub.7,
--CO--O--(CH.sub.2).sub.z--W--R.sub.7, a radical of the general
formula: ##STR00048## or
--(CH.sub.2).sub.z--V--(CH.sub.2).sub.z--CH.dbd.CH--R.sub.1, or
when S is --COOR.sub.5 or --COOM.sub.a, U.sub.1is --CO--NHM-, --O--
or --CH.sub.2O, U.sub.2 is --NH--CO--, --O-- or --OCH.sub.2, V is
--O--CO--C.sub.6H.sub.4--CO--O-- or --W--, and W is ##STR00049## R4
is a hydrogen atom or a methyl radical, R5 is an aliphatic
hydrocarbon radical containing 3 to 20 carbon atoms, a
cycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms
or an aryl radical containing 6 to 14 carbon atoms,
R.sub.6.dbd.R.sub.1 or ##STR00050## r is 2 to 100, s is 1 or 2, x
is 1 to 150, y is 0 to 15 and z is 0 to 4; iv) 0 to 90 mol % of at
least one component of the formula 6a, 6b, or 6c: ##STR00051##
wherein M is a hydrogen atom, a mono- or divalent metal cation, an
ammonium ion or an organic amine residue, a is 1, or when M is a
divalent metal cation a is 1/2; wherein X is --OM.sub.a,
--O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in which R.sup.1 is a
hydrogen atom, an aliphatic hydrocarbon radical containing from 1
to 20 carbon atoms, a cycloaliphatic hydrocarbon radical containing
5 to 8 carbon atoms or an optionally hydroxyl, carboxyl, C.sub.1-14
alkyl, or sulphonic substituted aryl radical containing 6 to 14
carbon atoms, m is 2 to 4, and n is 0 to 100,
--NH--(C.sub.mH.sub.2mO).sub.n--R.sup.1,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; j) a copolymer of dicarboxylic acid derivatives
and oxyalkylene glycol-alkenyl ethers, comprising: i) 1 to 90 mol.
% of at least one member selected from the group consisting of
structural units of formula 7a and formula 7b: ##STR00052## wherein
M is H, a monovalent metal cation, a divalent metal cation, an
ammonium ion or an organic amine; a is 1/2 when M is a divalent
metal cation or 1 when M is a monovalent metal cation; wherein
R.sup.1 is --OM.sub.a, or --O--(C.sub.mH.sub.2mO).sub.n--R.sup.2
wherein R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; ii) 0.5 to 80
mol. % of the structural units of formula 8: ##STR00053## wherein
R.sup.3 is H or a C.sub.1-5 aliphatic hydrocarbon; p is 0 to 3;
R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and --(PO.sub.3)
M.sub.a2; m is 2 to 4; n is 1 to 200; iii) 0.5 to 80 mol. %
structural units selected from the group consisting of formula 9a
and formula 9b: ##STR00054## wherein R.sup.4 is H, C.sub.1-20
aliphatic hydrocarbon that is optionally substituted with at least
one hydroxyl group, --(C.sub.mH.sub.2mO).sub.n--R.sup.2,
--CO--NH--R.sup.2, C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl that is optionally substituted with at least one
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2; M is H, a monovalent
metal cation, a divalent metal cation, an ammonium ion or an
organic amine; a is 1/2 when M is a divalent metal cation or 1 when
M is a monovalent metal cation; R.sup.2 is H, a C.sub.1-20
aliphatic hydrocarbon, a C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl that is optionally substituted with at least one
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1
to 200; iv) 1 to 90 mol. % of structural units of formula 10
##STR00055## wherein R.sup.5 is methyl, or methylene group, wherein
R.sup.5 forms one or more 5 to 8 membered rings with R.sup.7;
R.sup.6 is H, methyl, or ethyl; R.sup.7 is H, a C.sub.1-20
aliphatic hydrocarbon, a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2, a C.sub.5-8 cycloaliphatic hydrocarbon,
--OCOR.sup.4, --OR.sup.4, and --COOR.sup.4, wherein R.sup.4 is H, a
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one --OH, --(C.sub.mH.sub.2mO).sub.n--R.sup.2,
--CO--NH--R.sup.2, C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl residue that is optionally substituted with a
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2.
74. A method of making a colored cementitious composition without
increasing water demand comprising forming a mixture of hydraulic
cement and the liquid coloring suspension of claim 73.
75. A method of making a colored cementitious composition without
increasing water demand comprising forming a mixture of hydraulic
cement and a liquid coloring suspension, said liquid coloring
suspension comprising: a. liquid; b. polycarboxylate dispersant; c.
pigment; and d. thixotropic additive.
76. The method of claim 74 or 75 wherein the liquid comprises
water.
77. The method of claim 74 or 75 wherein the pigment comprises an
inorganic pigment.
78. The method of claim 77 wherein the inorganic pigment comprises
a metal containing pigment that comprises at least one of iron
oxide, chromium oxide, aluminum oxide, lead chromate, titanium
oxide, zinc white, zinc oxide, zinc sulfide, lead white, iron
manganese black, cobalt green, manganese blue, manganese violet,
cadmium sulfoselenide, chromium orange, nickel titanium yellow,
chromium titanium yellow, cadmium sulfide, zinc yellow, cobalt
blue, ultramarine blue or mixtures thereof.
79. The method of claim 74 or 75 wherein the pigment comprises an
organic pigment.
80. The method of claim 79 wherein the organic pigment comprises
phthalocyanine.
81. The method of claim 74 or 75 wherein the thixotropic additive
comprises at least one of organic flocculents, organic emulsions of
paraffin, coal tar, asphalt, acrylics, bentonite, pyrogenic
silicas, natural pozzolans, fly ash, hydrated lime, organoclay,
cellulose or mixtures thereof.
82. The method of claim 81 wherein the organoclay comprises at
least one of hectorite clay or smectite clay.
83. The method of claim 74 or 75, wherein the amount of
polycarboxylate dispersant solids are from about 0.0008% to about
0.51%, pigment solids are from about 0.1% to about 10%, and
thixotropic additive is from about 0.00008% to about 0.17%, by
total dry weight of cementitious binder.
84. The method of claim 74 or 75, wherein the amount of
polycarboxylate dispersant solids are from about 0.004% to about
0.25%, pigment solids are from about 0.25% to about 6%, and
thixotropic additive is from about 0.0004% to about 0.07%, by total
dry weight of cementitious binder.
85. The method of claim 76, wherein the water to cementitious
materials ratio is about 0.38 to about 0.65.
86. The method of claim 74 or 75, wherein the cement comprises at
least one of portland cement, modified portland cement, masonry
cement, or mixtures thereof.
87. The method of claim 74 or 75 further comprising a cement
admixture or additive that comprises at least one of set
accelerator, set retarder, air detraining agent, air entraining
agent, foaming agent, corrosion inhibitor, shrinkage reducing
admixture, water reducer, fiber, pozzolan, clay, strength enhancing
agents, rheology modifying agents, water repellents, wetting
agents, water soluble polymers, dampproofing admixtures, gas
formers, permeability reducers, pumping aids, fungicidal
admixtures, germicidal admixtures, insecticidal admixtures,
aggregates, alkali-reaction reducers, bonding admixtures, or
mixtures thereof.
88. The method of claim 87, wherein the aggregate comprises at
least one of silica, quartz, crushed round marble, glass spheres,
granite, limestone, calcite, feldspar, alluvial sands, or sand.
89. The method of claim 87, wherein the pozzolan comprises at least
one of natural pozzolan, metakaolin, fly ash, silica fume, calcined
clay, or blast furnace slag.
90. The liquid coloring suspension of claim 47 wherein the
polycarboxylate dispersant of the liquid coloring suspension is at
least one of: a) a dispersant of Formula (I): ##STR00056## wherein
in Formula (I) X is at least one of hydrogen, an alkali earth metal
ion, an alkaline earth metal ion, ammonium ion, or amine; R is at
least one of C.sub.1 to C.sub.6 alkyl(ene) ether or mixtures
thereof or C.sub.1 to C.sub.6 alkyl(ene) imine or mixtures thereof;
Q is at least one of oxygen, NH, or sulfur; p is a number from 1 to
about 300 resulting in at least one of a linear side chain or
branched side chain; R.sub.1 is at least one of hydrogen, C.sub.1
to C.sub.20 hydrocarbon, or functionalized hydrocarbon containing
at least one of --OH, --COOH, an ester or amide derivative of
--COOH, sulfonic acid, an ester or amide derivative of sulfonic
acid, amine, or epoxy; Y is at least one of hydrogen, an alkali
earth metal ion, an alkaline earth metal ion, ammonium ion, amine,
a hydrophobic hydrocarbon or polyalkylene oxide moiety that
functions as a defoamer; m, m', m'', n, n', and n'' are each
independently 0 or an integer between 1 and about 20; Z is a moiety
containing at least one of i) at least one amine and one acid
group, ii) two functional groups capable of incorporating into the
backbone selected from the group consisting of dianhydrides,
dialdehydes, and di-acid-chlorides, or iii) an imide residue; and
wherein a, b, c, and d reflect the mole fraction of each unit
wherein the sum of a, b, c, and d equal one, wherein a, b, c, and d
are each a value greater than or equal to zero and less than one,
and at least two of a, b, c, and d are greater than zero; b) a
dispersant of Formula (II): ##STR00057## wherein in Formula (II): A
is COOM or optionally in the "y" structure an acid anhydride group
(--CO--O--CO--) is formed in place of the A groups between the
carbon atoms to which the A groups are bonded to form an anhydride;
B is COOM M is hydrogen, a transition metal cation, the residue of
a hydrophobic polyalkylene glycol or polysiloxane, an alkali metal
ion, an alkaline earth metal ion, ferrous ion, aluminum ion,
(alkanol)ammonium ion, or (alkyl)ammonium ion; R is a C.sub.2-6
alkylene radical; R1 is a C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl,
or phenyl group; x, y, and z are a number from 0.01 to 100; m is a
number from 1 to 100; and n is a number from 10 to 100; c) a
dispersant comprising at least one polymer or a salt thereof having
the form of a copolymer of i) a maleic anhydride half-ester with a
compound of the formula RO(AO).sub.mH, wherein R is a
C.sub.1-C.sub.20 alkyl group, A is a C.sub.2-4 alkylene group, and
m is an integer from 2-16; and ii) a monomer having the formula
CH.sub.2.dbd.CHCH.sub.2--(OA).sub.nOR, wherein n is an integer from
1-90 and R is a C.sub.1-20 alkyl group; d) a dispersant obtained by
copolymerizing 5 to 98% by weight of an (alkoxy)polyalkylene glycol
mono(meth)acrylic ester monomer (a) represented by the following
general formula (1): ##STR00058## wherein R.sub.1 stands for
hydrogen atom or a methyl group, R.sub.2O for one species or a
mixture of two or more species of oxyalkylene group of 2 to 4
carbon atoms, providing two or more species of the mixture may be
added either in the form of a block or in a random form, R.sub.3
for a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m
is a value indicating the average addition mol number of
oxyalkylene groups that is an integer in the range of 1 to 100, 95
to 2% by weight of a (meth)acrylic acid monomer (b) represented by
the above general formula (2), wherein R.sub.4 and R.sub.5 are each
independently a hydrogen atom or a methyl group, and M.sub.1 for a
hydrogen atom, a monovalent metal atom, a divalent metal atom, an
ammonium group, or an organic amine group, and 0 to 50% by weight
of other monomer (c) copolymerizable with these monomers, provided
that the total amount of (a), (b), and (c) is 100% by weight; e) a
graft polymer that is a polycarboxylic acid or a salt thereof,
having side chains derived from at least one species selected from
the group consisting of oligoalkyleneglycols, polyalcohols,
polyoxyalkylene amines, and polyalkylene glycols; f) a dispersant
of Formula (III): ##STR00059## wherein in Formula (III): D=a
component selected from the group consisting of the structure d1,
the structure d2, and mixtures thereof; X=H, CH.sub.3, C.sub.2 to
C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl; Y=H
or --COOM; R=H or CH.sub.3; Z=H, --SO.sub.3M, --PO.sub.3M, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3, or
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, --CONHR.sub.3,
--CONHC(CH.sub.3).sub.2CH.sub.2SO.sub.3M, --COO(CHR.sub.4).sub.nOH
where n=2 to 6, or --O(CH.sub.2).sub.nOR.sub.4 wherein n=2 to 6;
R.sub.1, R.sub.2, R.sub.3, R.sub.5 are each independently
--(CHRCH.sub.2O).sub.mR.sub.4 random copolymer of oxyethylene units
and oxypropylene units where m=10 to 500 and wherein the amount of
oxyethylene in the random copolymer is from about 60% to 100% and
the amount of oxypropylene in the random copolymer is from 0% to
about 40%; R.sub.4=H, Methyl, C.sub.2 to about C.sub.6 Alkyl, or
about C.sub.6 to about C.sub.10 aryl; M=H, Alkali Metal, Alkaline
Earth Metal, Ammonium, Amine, triethanol amine, Methyl, or C.sub.2
to about C.sub.6 Alkyl; a=0 to about 0.8; b=about 0.2 to about 1.0;
c=0 to about 0.5; d=0 to about 0.5; and wherein a, b, c, and d
represent the mole fraction of each unit and the sum of a, b, c,
and d is 1.0; g) a dispersant of Formula (IV): ##STR00060## wherein
in Formula (IV): the "b" structure is one of a carboxylic acid
monomer, an ethylenically unsaturated monomer, or maleic anhydride
wherein an acid anhydride group (--CO--O--CO--) is formed in place
of the groups Y and Z between the carbon atoms to which the groups
Y and Z are bonded respectively, and the "b" structure must include
at least one moiety with a pendant ester linkage and at least one
moiety with a pendant amide linkage; X=H, CH.sub.3, C.sub.2 to
C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl, p-Ethyl Phenyl,
Carboxylated Phenyl, or Sulfonated Phenyl; Y=H, --COOM, --COOH, or
W; W=a hydrophobic defoamer represented by the formula
R.sub.5O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2C(CH.sub.3)HO).sub.t--(CH.s-
ub.2CH.sub.2O).sub.u where s, t, and u are integers from 0 to 200
with the proviso that t>(s+u) and wherein the total amount of
hydrophobic defoamer is present in an amount less than about 10% by
weight of the polycarboxylate dispersant; Z=H, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3,
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, or --CONHR.sub.3;
R.sub.1=H, or CH.sub.3; R.sub.2, R.sub.3, are each independently a
random copolymer of oxyethylene units and oxypropylene units of the
general formula --(CH(R.sub.1)CH.sub.2O).sub.mR.sub.4 where m=10 to
500 and wherein the amount of oxyethylene in the random copolymer
is from about 60% to 100% and the amount of oxypropylene in the
random copolymer is from 0% to about 40%; R.sub.4=H, Methyl, or
C.sub.2 to C.sub.8 Alkyl; R.sub.5.dbd.C.sub.1 to C.sub.18 alkyl or
C.sub.6 to C.sub.18 alkyl aryl; M=Alkali Metal, Alkaline Earth
Metal, Ammonia, Amine, monoethanol amine, diethanol amine,
triethanol amine, morpholine, imidazole; a=0.01-0.8; b=0.2-0.99;
c=0-0.5; and wherein a, b, c represent the mole fraction of each
unit and the sum of a, b, and c, is 1; h) a random copolymer
corresponding to the following Formula (V) in free acid or salt
form having the following monomer units and numbers of monomer
units: ##STR00061## wherein A is selected from the moieties (i) or
(ii) ##STR00062## (i) --CR.sub.1R.sub.2--CR.sub.3R.sub.4-- wherein
R.sub.1 and R.sub.3 are selected from substituted benzene,
C.sub.1-8 alkyl, C.sub.2-8 alkenyl, C.sub.2-8 alkylcarbonyl,
C.sub.1-8 alkoxy, carboxyl, hydrogen, and a ring, R.sub.2 and
R.sub.4 are selected from the group consisting of hydrogen and
C.sub.1-4 alkyl, wherein R.sub.1 and R.sub.3 can together with
R.sub.2 and/or R.sub.4 when R.sub.2 and/or R.sub.4 are C.sub.1-4
alkyl form the ring; R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are
individually selected from the group consisting of hydrogen,
C.sub.1-6 alkyl, and a C.sub.2-8 hydrocarbon chain, wherein R.sub.1
and R.sub.3 together with R.sub.7 and/or R.sub.8, R.sub.9, and
R.sub.10 form the C.sub.2-8 hydrocarbon chain joining the carbon
atoms to which they are attached, the hydrocarbon chain optionally
having at least one anionic group, wherein the at least one anionic
group is optionally sulfonic; M is selected from the group
consisting of hydrogen, and the residue of a hydrophobic
polyalkylene glycol or a polysiloxane, with the proviso that when A
is (ii) and M is the residue of a hydrophobic polyalkylene glycol,
M must be different from the group --(R.sub.5O).sub.mR.sub.6;
R.sub.5 is a C.sub.2-8 alkylene radical; R.sub.6 is selected from
the group consisting of C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl and
phenyl; n, x, and z are numbers from 1 to 100; y is 0 to 100; m is
2 to 1000; the ratio of x to (y+z) is from 1:10 to 10:1 and the
ratio of y:z is from 5:1 to 1:100; i) a copolymer of
oxyalkyleneglycol-alkenyl ethers and unsaturated dicarboxylic
acids, comprising: i) 0 to 90 mol % of at least one component of
the formula 3a or 3b: ##STR00063## wherein M is a hydrogen atom, a
mono- or divalent metal cation, an ammonium ion or an organic amine
residue, a is 1, or when M is a divalent metal cation a is 1/2;
wherein X is --OM.sub.a, --O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in
which R.sup.1 is a hydrogen atom, an aliphatic hydrocarbon radical
containing from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon
radical containing 5 to 8 carbon atoms or an optionally hydroxyl,
carboxyl, C.sub.1-14 alkyl, or sulphonic substituted aryl radical
containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; ii) 1 to 89 mol % of components of the general
formula 4: ##STR00064## wherein R.sub.3 is a hydrogen atom or an
aliphatic hydrocarbon radical containing from 1 to 5 carbon atoms,
p is 0 to 3, and R.sub.1 is hydrogen, an aliphatic hydrocarbon
radical containing from 1 to 20 carbon atoms, a cycloaliphatic
hydrocarbon radical containing 5 to 8 carbon atoms or an optionally
hydroxyl, carboxyl, C.sub.1-14 alkyl, or sulfonic substituted aryl
radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to
100, and iii) 0.1 to 10 mol % of at least one component of the
formula 5a or 5b: ##STR00065## wherein S is a hydrogen atom or
--COOM.sub.a or --COOR.sub.5, T is --COOR.sub.5, --W--R.sub.7,
--CO--[--NH--(CH2)3)-].sub.s-W--R.sub.7,
--CO--O--(CH.sub.2).sub.z--W--R.sub.7, a radical of the general
formula: ##STR00066## or
--(CH.sub.2).sub.z--V--(CH.sub.2).sub.z--CH.dbd.CH--R.sub.1, or
when S is --COOR.sub.5 or --COOM.sub.a, U.sub.1 is --CO--NHM-,
--O-- or --CH.sub.2O, U.sub.2 is --NH--CO--, --O-- or --OCH.sub.2,
V is --O--CO--C.sub.6H.sub.4--CO--O-- or --W--, and W is
##STR00067## R4 is a hydrogen atom or a methyl radical, R5 is an
aliphatic hydrocarbon radical containing 3 to 20 carbon atoms, a
cycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms
or an aryl radical containing 6 to 14 carbon atoms,
R.sub.6.dbd.R.sub.1 or ##STR00068## r is 2 to 100, s is 1 or 2, x
is 1 to 150, y is 0 to 15 and z is 0 to 4; iv) 0 to 90 mol % of at
least one component of the formula 6a, 6b, or 6c: ##STR00069##
wherein M is a hydrogen atom, a mono- or divalent metal cation, an
ammonium ion or an organic amine residue, a is 1, or when M is a
divalent metal cation a is 1/2; wherein X is --OM.sub.a,
--O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in which R.sup.1 is a
hydrogen atom, an aliphatic hydrocarbon radical containing from 1
to 20 carbon atoms, a cycloaliphatic hydrocarbon radical containing
5 to 8 carbon atoms or an optionally hydroxyl, carboxyl, C.sub.1-14
alkyl, or sulphonic substituted aryl radical containing 6 to 14
carbon atoms, m is 2 to 4, and n is 0 to 100,
--NH--(C.sub.mH.sub.2mO).sub.n--R.sup.1,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; j) a copolymer of dicarboxylic acid derivatives
and oxyalkylene glycol-alkenyl ethers, comprising: i) 1 to 90 mol.
% of at least one member selected from the group consisting of
structural units of formula 7a and formula 7b: ##STR00070## wherein
M is H, a monovalent metal cation, a divalent metal cation, an
ammonium ion or an organic amine; a is 1/2 when M is a divalent
metal cation or 1 when M is a monovalent metal cation; wherein
R.sup.1 is --OM.sub.a, or --O--(C.sub.mH.sub.2mO).sub.n--R.sup.2
wherein R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; ii) 0.5 to 80
mol. % of the structural units of formula 8: ##STR00071## wherein
R.sup.3 is H or a C.sub.1-5 aliphatic hydrocarbon; p is 0 to 3;
R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; iii) 0.5 to 80
mol. % structural units selected from the group consisting of
formula 9a and formula 9b: ##STR00072## wherein R.sup.4 is H,
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one hydroxyl group,
--(C.sub.mH.sub.2mO).sub.n--R.sup.2, --CO--NH--R.sup.2, C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; M is H, a monovalent metal cation, a divalent
metal cation, an ammonium ion or an organic amine; a is 1/2 when M
is a divalent metal cation or 1 when M is a monovalent metal
cation; R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; iv) 1 to 90 mol.
% of structural units of formula 10 ##STR00073## wherein R.sup.5 is
methyl, or methylene group, wherein R.sup.5 forms one or more 5 to
8 membered rings with R.sup.7; R.sup.6 is H, methyl, or ethyl;
R.sup.7 is H, a C.sub.1-20 aliphatic hydrocarbon, a C.sub.6-14 aryl
that is optionally substituted with at least one member selected
from the group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2, a C.sub.5-8 cycloaliphatic hydrocarbon,
--OCOR.sup.4, --OR.sup.4, and --COOR.sup.4, wherein R.sup.4 is H, a
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one --OH, --(C.sub.mH.sub.2mO).sub.n--R.sup.2,
--CO--NH--R.sup.2, C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl residue that is optionally substituted with a
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2.
Description
BACKGROUND
A pigment, as related to its use in concrete, mortar and cement
paste is defined as a fine dry powder, dry granules, aqueous
suspension, or slurry, of the powder or granules, insoluble and
inert to the concrete ingredients and which imparts a specific
color to the product. The color of a pigment can be described in
terms of three properties: hue, value, and chroma, which are
indicative of the purity (oxide content) and the brightness of the
pigment.
Pigments in the dry form exist as agglomerates of particles. The
ease with which the aggregates are broken down and dispersed in
concrete, mortar and cement paste depends on the extent to which
the forces of attraction between the particles is reduced. The
coloring action of pigments is dependent on the extent of smearing
over the cement and fine aggregate in the mix. Therefore, cement
and fine aggregate contents will significantly influence the degree
of coloration achieved.
Dosages of pigments typically decrease slump, increase the water
demand and premature stiffening of the cementitious composition and
may produce flash setting. To increase the slump of the
cementitious mixture additional water is added, however, in general
the higher the water content of the mix, the lighter will be the
final color. The increased water content also decreases the
strength of the resulting cementitious composition.
Therefore, it is desirable to provide a colored cementitious
composition comprising a liquid coloring suspension which contains
a dispersant and a pigment that improves the color, increases or
has no effect on slump, and lowers or has no effect on the water
demand of the cementitious composition. Therefore, a liquid
coloring suspension which improves the color of cementitious
compositions without increasing the water content or decreasing
slump would be advantageous in the industry.
U.S. Pat. No. 5,853,476 to Will discloses a method for coloring
cementitious systems using compacted inorganic granules, wherein
the compacted inorganic granules comprise an inorganic pigment and
a non-polycarboxylate dispersing agent.
U.S. Pat. No. 4,514,947 to Grail discloses a roof tile made of a
composition of matter comprising cement, silica sand, iron oxide
pigment, acrylic polymer resin, an antifoaming agent and water and
formed into a shape.
U.S. Pat. No. 4,714,781 to De Witte discloses iron oxide slurries
and suspensions that are made from water, iron oxide pigments and a
non-polycarboxylate dispersing agents such as water soluble salts
of citric acid and tartaric acid.
SUMMARY
A method of making a colored cementitious composition without
increasing water demand is provided which comprises forming a
mixture of hydraulic cement and a liquid coloring suspension,
wherein the liquid coloring suspension comprises liquid,
polycarboxylate dispersant and pigment.
A colored cementitious composition is provided that comprises a
hydraulic cement and a liquid coloring suspension that comprises
liquid, polycarboxylate dispersant and pigment, and wherein the
liquid coloring suspension improves the color in the cementitious
composition without increasing the water demand.
A liquid coloring suspension is provided that comprises
polycarboxylate dispersant, pigment and thixotropic additive,
wherein the viscosity of the liquid coloring suspension is stable
over time.
A colored cementitious composition is provided that comprises
hydraulic cement and a liquid coloring suspension that comprises
liquid, polycarboxylate dispersant, pigment, and thixotropic
additive, wherein the liquid coloring suspension improves the color
in the cementitious composition without increasing the water
demand.
A method of making a colored cementitious composition without
increasing water demand is provided which comprises forming a
mixture of hydraulic cement and a liquid coloring suspension,
wherein the liquid coloring suspension comprises liquid,
polycarboxylate dispersant, pigment and thixotropic additive.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 demonstrates the long term stability of the liquid coloring
suspension at 50.degree. F., in that there was no increase in the
viscosity of the suspension over time (5 months).
FIG. 2 demonstrates the long term stability of the liquid coloring
suspension at 70.degree. F., in that there was no increase in the
viscosity of the suspension over time (5 months).
FIG. 3 demonstrates the long term stability of the liquid coloring
suspension at 90.degree. F., in that there was no increase in the
viscosity of the suspension over time (5 months).
DETAILED DESCRIPTION
A liquid coloring suspension is provided that has long term
stability, reduces the water content and viscosity of cementitious
compositions and increases the color by improving pigment
dispersion throughout the mixture. A cementitious composition
containing the liquid coloring suspension is also provided, as well
as a novel method for preparing such a colored cementitious
composition.
In contrast to conventional pigmented cementitious formulations,
made by mixing hydraulic cement, a pigment dispersant and a
powdered pigment or a dispersion thereof, cementitious formulations
made by mixing a hydraulic cement and a liquid coloring suspension
comprising a dispersion of a polycarboxylate and a pigment,
synergistically exhibit water neutrality or decreased, rather than
increased water demand. These pigmented cementitious formulations
also exhibit excellent compressive strength after set, and no
retardation of set compared to a corresponding non-pigmented
formulations. The cementitious formulation made according to the
present method exhibits increased color strength compared to
conventional pigmented concretes.
A colored cementitious composition which has a liquid coloring
suspension is provided that has improved color dispersion and a
neutral or reduced water content, as well as a novel method for
preparing such a colored cementitious composition.
Polycarboxylate dispersants are effective at dispersing cement and
reducing the water content in hydraulic cementitious compositions.
These dispersants operate by binding to a cement particle and
developing both electrostatic and steric repulsive forces, thereby
keeping the particles apart, resulting in a more fluid system.
The term polycarboxylate dispersant used throughout this
specification refers to polymers with a carbon backbone with
pendant side chains, wherein at least a portion of the side chains
are attached to the backbone through a carboxyl group or an ether
group. The term dispersant is also meant to include those chemicals
which also function as a plasticizer, water reducer, fluidizer,
antiflocculating agent, or superplasticizer for cementitious
compositions. Examples of polycarboxylate dispersants can be found
in U.S. Pub. No. 2002/0019459 A1, U.S. Pat. Nos. 6,267,814,
6,290,770, 6,310,143, 6,187,841, 5,158,996, 6,008,275, 6,136,950,
6,284,867, 5,609,681, 5,494,516; 5,674,929,5,660,626, 5,668,195,
5,661,206, 5,358,566, 5,162,402, 5,798,425, 5,612,396, 6,063,184,
5,912,284, 5,840,114, 5,753,744, 5,728,207, 5,725,657, 5,703,174,
5,665,158, 5,643,978, 5,633,298, 5,583,183, and 5,393,343, which
are all incorporated herein by reference.
In one embodiment the admixture composition contains about 0.5% to
about 3% polycarboxylate dispersant solids based on the total
weight of the liquid coloring suspension. In another embodiment the
admixture composition contains about 1% to about 2.5%
polycarboxylate dispersant solids based on the total weight of the
liquid coloring suspension. In another embodiment a cementitious
composition contains about 0.0008% to about 0.51% polycarboxylate
dispersant solids by dry weight of cementitious binder. In a
further embodiment a cementitious composition contains about 0.004%
to about 0.25% polycarboxylate dispersant solids by dry weight of
cementitious binder.
The polycarboxylate dispersants used in the system can be at least
one of the dispersant formulas a) through k):
a) a dispersant of Formula (I):
##STR00001## wherein in Formula (I) X is at least one of hydrogen,
an alkali earth metal ion, an alkaline earth metal ion, ammonium
ion, or amine; R is at least one of C.sub.1 to C.sub.6 alkyl(ene)
ether or mixtures thereof or C.sub.1 to C.sub.6 alkyl(ene) imine or
mixtures thereof; Q is at least one of oxygen, NH, or sulfur; p is
a number from 1 to about 300 resulting in at least one of a linear
side chain or branched side chain; R.sub.1 is at least one of
hydrogen, C.sub.1 to C.sub.20 hydrocarbon, or functionalized
hydrocarbon containing at least one of --OH, --COOH, an ester or
amide derivative of --COOH, sulfonic acid, an ester or amide
derivative of sulfonic acid, amine, or epoxy; Y is at least one of
hydrogen, an alkali earth metal ion, an alkaline earth metal ion,
ammonium ion, amine, a hydrophobic hydrocarbon or polyalkylene
oxide moiety that functions as a defoamer; m, m', m'', n, n', and
n'' are each independently 0 or an integer between 1 and about 20;
Z is a moiety containing at least one of i) at least one amine and
one acid group, ii) two functional groups capable of incorporating
into the backbone selected from the group consisting of
dianhydrides, dialdehydes, and di-acid-chlorides, or iii) an imide
residue; and wherein a, b, c, and d reflect the mole fraction of
each unit wherein the sum of a, b, c, and d equal one, wherein a,
b, c, and d are each a value greater than or equal to zero and less
than one, and at least two of a, b, c, and d are greater than zero;
b) a dispersant of Formula (II):
##STR00002## wherein in Formula (II): A is COOM or optionally in
the "y" structure an acid anhydride group (--CO--O--CO--) is formed
in place of the A groups between the carbon atoms to which the A
groups are bonded to form an anhydride; B is COOM M is hydrogen, a
transition metal cation, the residue of a hydrophobic polyalkylene
glycol or polysiloxane, an alkali metal ion, an alkaline earth
metal ion, ferrous ion, aluminum ion, (alkanol)ammonium ion, or
(alkyl)ammonium ion; R is a C.sub.2-6 alkylene radical; R1 is a
C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl, or phenyl group; x, y, and
z are a number from 0.01 to 100; m is a number from 1 to 100; and n
is a number from 10 to 100; c) a dispersant comprising at least one
polymer or a salt thereof having the form of a copolymer of i) a
maleic anhydride half-ester with a compound of the formula
RO(AO).sub.mH, wherein R is a C.sub.1-C.sub.20 alkyl group, A is a
C.sub.2-4 alkylene group, and m is an integer from 2-16; and ii) a
monomer having the formula CH.sub.2.dbd.CHCH.sub.2--(OA).sub.nOR,
wherein n is an integer from 1-90 and R is a C.sub.1-20 alkyl
group; d) a dispersant obtained by copolymerizing 5 to 98% by
weight of an (alkoxy)polyalkylene glycol mono(meth)acrylic ester
monomer (a) represented by the following general formula (1):
##STR00003## wherein R.sub.1 stands for hydrogen atom or a methyl
group, R.sub.2O for one species or a mixture of two or more species
of oxyalkylene group of 2 to 4 carbon atoms, providing two or more
species of the mixture may be added either in the form of a block
or in a random form, R.sub.3 for a hydrogen atom or an alkyl group
of 1 to 5 carbon atoms, and m is a value indicating the average
addition mol number of oxyalkylene groups that is an integer in the
range of 1 to 100, 95 to 2% by weight of a (meth)acrylic acid
monomer (b) represented by the above general formula (2), wherein
R.sub.4 and R.sub.5 are each independently a hydrogen atom or a
methyl group, and M.sub.1 for a hydrogen atom, a monovalent metal
atom, a divalent metal atom, an ammonium group, or an organic amine
group, and 0 to 50% by weight of other monomer (c) copolymerizable
with these monomers, provided that the total amount of (a), (b),
and (c) is 100% by weight; e) a graft polymer that is a
polycarboxylic acid or a salt thereof, having side chains derived
from at least one species selected from the group consisting of
oligoalkyleneglycols, polyalcohols, polyoxyalkylene amines, and
polyalkylene glycols; f) a dispersant of Formula (III):
##STR00004## wherein in Formula (III): D=a component selected from
the group consisting of the structure d1, the structure d2, and
mixtures thereof; X=H, CH.sub.3, C.sub.2 to C.sub.6 Alkyl, Phenyl,
p-Methyl Phenyl, or Sulfonated Phenyl; Y=H or --COOM; R=H or
CH.sub.3; Z=H, --SO.sub.3M, --PO.sub.3M, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3, or
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, --CONHR.sub.3,
--CONHC(CH.sub.3).sub.2CH.sub.2SO.sub.3M, --COO(CHR.sub.4).sub.nOH
where n=2 to 6, or --O(CH.sub.2).sub.nOR.sub.4 wherein n=2 to 6;
R.sub.1, R.sub.2, R.sub.3, R.sub.5 are each independently
--(CHRCH.sub.2O).sub.mR.sub.4 random copolymer of oxyethylene units
and oxypropylene units where m=10 to 500 and wherein the amount of
oxyethylene in the random copolymer is from about 60% to 100% and
the amount of oxypropylene in the random copolymer is from 0% to
about 40%; R.sub.4=H, Methyl, C.sub.2 to about C.sub.6 Alkyl, or
about C.sub.6 to about C.sub.10 aryl; M=H, Alkali Metal, Alkaline
Earth Metal, Ammonium, Amine, triethanol amine, Methyl, or C.sub.2
to about C.sub.6 Alkyl; a=0 to about 0.8; b=about 0.2 to about 1.0;
c=0 to about 0.5; d=0 to about 0.5; and wherein a, b, c, and d
represent the mole fraction of each unit and the sum of a, b, c,
and d is 1.0; g) a dispersant of Formula (IV):
##STR00005## wherein in Formula (IV): the "b" structure is one of a
carboxylic acid monomer, an ethylenically unsaturated monomer, or
maleic anhydride wherein an acid anhydride group (--CO--O--CO--) is
formed in place of the groups Y and Z between the carbon atoms to
which the groups Y and Z are bonded respectively, and the "b"
structure must include at least one moiety with a pendant ester
linkage and at least one moiety with a pendant amide linkage; X=H,
CH.sub.3, C.sub.2 to C.sub.6 Alkyl, Phenyl, p-Methyl Phenyl,
p-Ethyl Phenyl, Carboxylated Phenyl, or Sulfonated Phenyl; Y=H,
--COOM, --COOH, or W; W=a hydrophobic defoamer represented by the
formula
R.sub.5O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2C(CH.sub.3)HO).sub.t--(CH.s-
ub.2CH.sub.2O).sub.u where s, t, and u are integers from 0 to 200
with the proviso that t>(s+u) and wherein the total amount of
hydrophobic defoamer is present in an amount less than about 10% by
weight of the polycarboxylate dispersant; Z=H, --COOM,
--O(CH.sub.2).sub.nOR.sub.3 where n=2 to 6, --COOR.sub.3,
--(CH.sub.2).sub.nOR.sub.3 where n=0 to 6, or --CONHR.sub.3;
R.sub.1=H, or CH.sub.3; R.sub.2, R.sub.3, are each independently a
random copolymer of oxyethylene units and oxypropylene units of the
general formula --(CH(R.sub.1)CH.sub.2O).sub.mR.sub.4 where m=10 to
500 and wherein the amount of oxyethylene in the random copolymer
is from about 60% to 100% and the amount of oxypropylene in the
random copolymer is from 0% to about 40%; R.sub.4=H, Methyl, or
C.sub.2 to C.sub.8 Alkyl; R.sub.5=C.sub.1 to C.sub.18 alkyl or
C.sub.6 to C.sub.18 alkyl aryl; M=Alkali Metal, Alkaline Earth
Metal, Ammonia, Amine, monoethanol amine, diethanol amine,
triethanol amine, morpholine, imidazole; a=0.01-0.8; b=0.2-0.99;
c=0-0.5; and wherein a, b, c represent the mole fraction of each
unit and the sum of a, b, and c, is 1; h) a random copolymer
corresponding to the following Formula (V) in free acid or salt
form having the following monomer units and numbers of monomer
units:
##STR00006## wherein A is selected from the moieties (i) or
(ii)
##STR00007## (i) --CR.sub.1R.sub.2--CR.sub.3R.sub.4-- (ii) wherein
R.sub.1 and R.sub.3 are selected from substituted benzene,
C.sub.1-8 alkyl, C.sub.2-8 alkenyl, C.sub.2-8 alkylcarbonyl,
C.sub.1-8 alkoxy, carboxyl, hydrogen, and a ring, R.sub.2 and
R.sub.4 are selected from the group consisting of hydrogen and
C.sub.1-4 alkyl, wherein R.sub.1 and R.sub.3 can together with
R.sub.2 and/or R.sub.4 when R.sub.2 and/or R.sub.4 are C.sub.1-4
alkyl form the ring; R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are
individually selected from the group consisting of hydrogen,
C.sub.1-6 alkyl, and a C.sub.2-8 hydrocarbon chain, wherein R.sub.1
and R.sub.3 together with R.sub.7 and/or R.sub.8, R.sub.9, and
R.sub.10 form the C.sub.2-8 hydrocarbon chain joining the carbon
atoms to which they are attached, the hydrocarbon chain optionally
having at least one anionic group, wherein the at least one anionic
group is optionally sulfonic; M is selected from the group
consisting of hydrogen, and the residue of a hydrophobic
polyalkylene glycol or a polysiloxane, with the proviso that when A
is (ii) and M is the residue of a hydrophobic polyalkylene glycol,
M must be different from the group --(R.sub.5O).sub.mR.sub.6;
R.sub.5 is a C.sub.2-8 alkylene radical; R.sub.6 is selected from
the group consisting of C.sub.1-20 alkyl, C.sub.6-9 cycloalkyl and
phenyl; n, x, and z are numbers from 1 to 100; y is 0 to 100; m is
2 to 1000; the ratio of x to (y+z) is from 1:10 to 10:1 and the
ratio of y:z is from 5:1 to 1:100; i) a copolymer of
oxyalkyleneglycol-alkenyl ethers and unsaturated dicarboxylic
acids, comprising: i) 0 to 90 mol % of at least one component of
the formula 3a or 3b:
##STR00008## wherein M is a hydrogen atom, a mono- or divalent
metal cation, an ammonium ion or an organic amine residue, a is 1,
or when M is a divalent metal cation a is 1/2; wherein X is
--OM.sub.a, --O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in which R.sup.1
is a hydrogen atom, an aliphatic hydrocarbon radical containing
from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical
containing 5 to 8 carbon atoms or an optionally hydroxyl, carboxyl,
C.sub.1-14 alkyl, or sulphonic substituted aryl radical containing
6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; ii) 1 to 89 mol % of components of the general
formula 4:
##STR00009## wherein R.sub.3 is a hydrogen atom or an aliphatic
hydrocarbon radical containing from 1 to 5 carbon atoms, p is 0 to
3, and R.sub.1 is hydrogen, an aliphatic hydrocarbon radical
containing from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon
radical containing 5 to 8 carbon atoms or an optionally hydroxyl,
carboxyl, C.sub.1-14 alkyl, or sulfonic substituted aryl radical
containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
and iii) 0.1 to 10 mol % of at least one component of the formula
5a or 5b:
##STR00010## wherein S is a hydrogen atom or --COOM.sub.a or
--COOR.sub.5, T is --COOR.sub.5, --W--R.sub.7,
--CO--[--NH--(CH2)3)-].sub.s--W--R.sub.7,
--CO--O--(CH.sub.2).sub.z--W--R.sub.7, a radical of the general
formula:
##STR00011## or
--(CH.sub.2).sub.z--V--(CH.sub.2).sub.z--CH.dbd.CH--R.sub.1, or
when S is --COOR.sub.5 or --COOM.sub.a, U.sub.1 is --CO--NHM-,
--O-- or --CH.sub.2O, U.sub.2 is --NH--CO--, --O-- or --OCH.sub.2,
V is --O--CO--C.sub.6H.sub.4--CO--O-- or --W--, and W is
##STR00012## R4 is a hydrogen atom or a methyl radical, R5 is an
aliphatic hydrocarbon radical containing 3 to 20 carbon atoms, a
cycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms
or an aryl radical containing 6 to 14 carbon atoms,
R.sub.6.dbd.R.sub.1 or
##STR00013## r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to
15 and z is 0 to 4; iv) 0 to 90 mol % of at least one component of
the formula 6a, 6b, or 6c:
##STR00014## wherein M is a hydrogen atom, a mono- or divalent
metal cation, an ammonium ion or an organic amine residue, a is 1,
or when M is a divalent metal cation a is 1/2; wherein X is
--OM.sub.a, --O--(C.sub.mH.sub.2mO).sub.n--R.sup.1 in which R.sup.1
is a hydrogen atom, an aliphatic hydrocarbon radical containing
from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical
containing 5 to 8 carbon atoms or an optionally hydroxyl, carboxyl,
C.sub.1-14 alkyl, or sulphonic substituted aryl radical containing
6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,
--NH--(C.sub.mH.sub.2mO).sub.n--R.sup.1,
--NHR.sub.2,--N(R.sup.2).sub.2 or mixtures thereof in which
R.sup.2.dbd.R.sup.1 or --CO--NH.sub.2; and wherein Y is an oxygen
atom or --NR.sup.2; j) a copolymer of dicarboxylic acid derivatives
and oxyalkylene glycol-alkenyl ethers, comprising: i) 1 to 90 mol.
% of at least one member selected from the group consisting of
structural units of formula 7a and formula 7b:
##STR00015## wherein M is H, a monovalent metal cation, a divalent
metal cation, an ammonium ion or an organic amine; a is 1/2 when M
is a divalent metal cation or 1 when M is a monovalent metal
cation; wherein R.sup.1 is --OM.sub.a, or
--O--(C.sub.mH.sub.2mO).sub.n--R.sup.2 wherein R.sup.2 is H, a
C.sub.1-20 aliphatic hydrocarbon, a C.sub.5-8 cycloaliphatic
hydrocarbon, or a C.sub.6-14 aryl that is optionally substituted
with at least one member selected from the group consisting of
--COOM.sub.a, --(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2; m is 2
to 4; n is 1 to 200; ii) 0.5 to 80 mol. % of the structural units
of formula 8:
##STR00016## wherein R.sup.3 is H or a C.sub.1-5 aliphatic
hydrocarbon; p is 0 to 3; R.sup.2 is H, a C.sub.1-20 aliphatic
hydrocarbon, a C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl that is optionally substituted with at least one
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3) M.sub.a2; m is 2 to 4; n is 1
to 200; iii) 0.5 to 80 mol. % structural units selected from the
group consisting of formula 9a and formula 9b:
##STR00017## wherein R.sup.4 is H, C.sub.1-20 aliphatic hydrocarbon
that is optionally substituted with at least one hydroxyl group,
--(C.sub.mH.sub.2mO).sub.n--R.sup.2, --CO--NH--R.sup.2, C.sub.5-8
cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; M is H, a monovalent metal cation, a divalent
metal cation, an ammonium ion or an organic amine; a is 1/2 when M
is a divalent metal cation or 1 when M is a monovalent metal
cation; R.sup.2 is H, a C.sub.1-20 aliphatic hydrocarbon, a
C.sub.5-8 cycloaliphatic hydrocarbon, or a C.sub.6-14 aryl that is
optionally substituted with at least one member selected from the
group consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2; m is 2 to 4; n is 1 to 200; iv) 1 to 90 mol.
% of structural units of formula 10
##STR00018## wherein R.sup.5 is methyl, or methylene group, wherein
R.sup.5 forms one or more 5 to 8 membered rings with R.sup.7;
R.sup.6 is H, methyl, or ethyl; R.sup.7 is H, a C.sub.1-20
aliphatic hydrocarbon, a C.sub.6-14 aryl that is optionally
substituted with at least one member selected from the group
consisting of --COOM.sub.a, --(SO.sub.3)M.sub.a, and
--(PO.sub.3)M.sub.a2, a C.sub.5-8 cycloaliphatic hydrocarbon,
--OCOR.sup.4, --OR.sup.4, and --COOR.sup.4, wherein R.sup.4 is H, a
C.sub.1-20 aliphatic hydrocarbon that is optionally substituted
with at least one --OH, --(C.sub.mH.sub.2mO).sub.n--R.sup.2,
--CO--NH--R.sup.2, C.sub.5-8 cycloaliphatic hydrocarbon, or a
C.sub.6-14 aryl residue that is optionally substituted with a
member selected from the group consisting of --COOM.sub.a,
--(SO.sub.3)M.sub.a, and --(PO.sub.3)M.sub.a2.
In formula (e) the word "derived" does not refer to derivatives in
general, but rather to any polycarboxylic acid/salt side chain
derivatives of oligoalkyleneglycols, polyalcohols and polyalkylene
glycols that are compatible with dispersant properties and do not
destroy the graft polymer.
The preferred substituents in the optionally substituted aryl
radical of formula (i), containing 6 to 14 carbon atoms, are
hydroxyl, carboxyl, C.sub.1-14 alkyl, or sulfonate groups.
The preferred substituents in the substituted benzene are hydroxyl,
carboxyl, C.sub.1-14 alkyl, or sulfonate groups.
Coloring admixtures in the form of slurries or dispersions are used
for four main reasons: (a) to enhance the wetting and dispersion
characteristics of materials containing very fine particles with
inherently poor wettability; (b) enable dispersion through commonly
used equipment; (c) for easier addition to concrete transportation
vehicles due to pigment slurry providing uniformly colored concrete
mixtures; and (d) to reduce health hazards that may result by
handling fine powders. These coloring admixtures are usually
composed of pigments, either organic such as phthalocyanine or
inorganic pigments such as metal-containing pigments that comprise,
but are not limited to metal oxides and others, and can include,
but are not limited to, iron oxide containing pigments such as
CHROMIX.RTM.L (MasterBuilders, Cleveland Ohio), chromium oxide,
aluminum oxide, lead chromate, titanium oxide, zinc white, zinc
oxide, zinc sulfide, lead white, iron manganese black, cobalt
green, manganese blue, manganese violet, cadmium sulfoselenide,
chromium orange, nickel titanium yellow, chromium titanium yellow,
cadmium sulfide, zinc yellow, ultramarine blue and cobalt blue.
The color of a pigment can be described in terms of three
properties: hue, value, and chroma, which are indicative of the
purity (oxide content) and the brightness of the pigment. Hue is
the property of a color which distinguishes red from yellow, blue,
etc. Value or lightness denotes the light reflecting quality or
lightness of a color. Chroma or saturation is the richness or depth
of hue or a color and is a measure of its departure from a gray or
neutral of equal value.
In one embodiment the liquid coloring suspension contains about 50%
to about 75% pigment solids based on the total weight of the liquid
coloring suspension. In another embodiment the liquid coloring
suspension composition contains about 53% %to about 70% pigment
solids based on the total weight of the liquid coloring suspension.
In another embodiment a cementitious composition contains about
0.1% to about 10% pigment solids by dry weight of cementitious
binder. In a further embodiment a cementitious composition contains
about 0.25% to about 6% pigment solids by dry weight of
cementitious binder.
The pigment dispersions (liquid coloring suspensions) of the prior
art do not effectively disperse the pigment particles in cement and
concrete mixtures, particularly when the concentration of pigment
in the liquid coloring suspension is high (admixture composition
with greater than 55% pigment solids). Additionally, as the
concentration of pigment in the liquid coloring suspension
increases, the pigment particles begin to separate and settle out
of solution providing a poor storage life for the admixture. There
are metal containing (iron oxide) pigment dispersions in the prior
art with higher than 50% pigment solids, but these dispersions have
been formulated for paints or plastics and have negative effects in
cement and concrete such as increasing entrapped air. In
cementitious mixtures, elevated air decreases design yield and
compressive strength, and causes other deleterious effects.
The liquid coloring suspension which contains a polycarboxylate
dispersant, improves the dispersion of pigment particles in
cementitious compositions when compared to the coloring admixtures
in the prior art. Addition of pigment dispersions to cementitious
compositions conventionally increases the water demand and
decreases the slump, which is one measure of the consistency of
concrete. This increase in water demand becomes greater at higher
doses of liquid coloring suspension, especially as the
concentration of pigment particles in the pigment dispersion
increases. In contrast, the liquid coloring suspension of the
present invention does not increase the water demand of the
cementitious composition even when dosed at high concentrations by
weight of cement. Further, the pigment dispersion improves the
color of cementitious compositions.
Metal containing (iron oxide) pigment dispersions in the prior art
with higher than 50% pigment solids tend to gain viscosity over
time which leads to gel formation and decreased shelf life. In
addition, some pigment dispersions (liquid coloring suspensions) of
the prior art effectively disperse the pigment particles in cement
and concrete mixtures but often cause negative effects such as
increasing entrapped air. In cementitious mixtures, elevated air
decreases compressive strength, makes finishing more difficult, and
causes other deleterious effects.
Thixotropic additives decrease pigment separation and settling in
liquid coloring suspensions and induce them to thicken up rapidly
to form gel structures, i.e., increase its viscosity. The gel
structures are self supporting and lower the hydrostatic pressure
to the formation as gel strength increases. Thixotropic additives
can be organic and synthetic polymers, cellulose or cellulose
blended with dispersants, organic flocculents, organic emulsions of
paraffin, coal tar, asphalt, acrylics, bentonite and pyrogenic
silicas, natural pozzolans, fly ash, hydrated lime, and organoclays
such as hectorite clay or smectite clay.
In one embodiment the liquid coloring suspension contains about
0.05% to about 1% thixotropic additive based on the total weight of
the liquid coloring suspension. In another embodiment the liquid
coloring suspension contains about 0.1% to about 0.70% thixotropic
additive based on the total weight of the liquid coloring
suspension. In another embodiment a cementitious composition
contains about 0.00008% to about 0.17% thixotropic additive by
total dry weight of cementitious binder. In a further embodiment a
cementitious composition contains about 0.0004% to about 0.07%
thixotropic additive by total dry weight of cementitious
binder.
While not being limited to theory it is thought that there is a
negative synergistic effect caused by the interaction of the
polycarboxylate dispersant with the thixotropic additive, as it
would be expected based on the prior art that the thixotropic
additive would increase the viscosity of the liquid coloring
suspension when compared to a liquid coloring suspension containing
polycarboxylate dispersant and pigment alone. However, the liquid
coloring suspension containing the thixotropic additive has the
unexpected result of having a lower viscosity than that of the
admixture containing polycarboxylate dispersant and pigment alone,
coupled with long term stability (low viscosity). Additionally, as
compared to the pigment dispersions of the prior art where the
viscosity increases over time causing gelling, the viscosity of the
liquid coloring suspension decreases then stabilizes over time.
Based on the prior art, it is expected that a liquid coloring
suspension, used to impart color to a cementitious composition,
containing a dispersant and thixotrope additive would increase in
viscosity over time causing the liquid coloring suspension to gel.
In the present instance, there is an unexpected synergistic effect
due to the interaction of the polycarboxylate dispersant with the
thixotropic additive that causes the viscosity of the liquid
coloring suspension to decrease, then stabilize over time. This
results in increased shelf life stability of the liquid coloring
suspension.
The hydraulic cement comprising the cementitious composition is
selected from the group consisting of portland cement, modified
portland cement, or masonry cement, and mixtures thereof. By
portland cement is meant all cementitious compositions which have a
high content of tricalcium silicate and includes portland cement
and cements that are chemically similar or analogous to portland
cement, the specification for which is set forth in ASTM
specification C 150-00.
Cementitious materials are materials that alone have hydraulic
cementing properties, and set and harden in the presence of water.
Included in cementitious materials are ground granulated
blast-furnace slag, natural cement, hydraulic hydrated lime, and
combinations of these and other materials.
The cementitious composition described herein may contain other
additives or ingredients and should not be limited to the stated
formulations. Cement additives that can be added include, but are
not limited to: set accelerators, set retarders, air-entraining or
air detraining agents, water reducers, corrosion inhibitors,
wetting agents, water soluble polymers, strength enhancing agents,
rheology modifying agents, water repellents, fibers, dampproofing
admixtures, gas formers, permeability reducers, pumping aids,
fungicidal admixtures, germicidal admixtures, insecticidal
admixtures, finely divided mineral admixtures, alkali-reactivity
reducer, bonding admixtures, shrinkage reducing admixtures,
aggregate, pozzolan and any other admixture or additive that does
not adversely affect the properties of the liquid coloring
suspension or cementitious composition.
An accelerator that can be used in the liquid coloring suspension
can include, but is not limited to, a nitrate salt of an alkali
metal, alkaline earth metal, or aluminum; a nitrite salt of an
alkali metal, alkaline earth metal, or aluminum; a thiocyanate of
an alkali metal, alkaline earth metal or aluminum; an alkanolamine;
a thiosulphate of an alkali metal, alkaline earth metal, or
aluminum; a hydroxide of an alkali metal, alkaline earth metal, or
aluminum; a carboxylic acid salt of an alkali metal, alkaline earth
metal, or aluminum (preferably calcium formate); a
polyhydroxylalkylamine; a halide salt of an alkali metal or
alkaline earth metal (preferably bromide), Examples of accelerators
that can be used include, but are not limited to, POZZOLITH.RTM.
NC534, nonchloride type accelerator and/or RHEOCRETE.RTM. CNI
calcium nitrite-based corrosion inhibitor both sold under the
trademarks by Master Builders Inc. of Cleveland, Ohio.
The salts of nitric acid have the general formula M(NO.sub.3).sub.a
where M is an alkali metal, or an alkaline earth metal or aluminum,
and where a is 1 for alkali metal salts, 2 for alkaline earth
salts, and 3 for aluminum salts. Preferred are nitric acid salts of
Na, K, Mg, Ca and Al.
Nitrite salts have the general formula M(NO.sub.2).sub.a where M is
an alkali metal, or an alkaline earth metal or aluminum, and where
a is 1 for alkali metal salts, 2 for alkaline earth salts, and 3
for aluminum salts. Preferred are nitric acid salts of Na, K, Mg,
Ca and Al.
The salts of the thiocyanic acid have the general formula
M(SCN).sub.b, where M is an alkali metal, or an alkaline earth
metal or aluminum, and where b is 1 for alkali metal salts, 2 for
alkaline earth salts and 3 for aluminum salts. These salts are
variously known as sulfocyanates, sulfocyanides, rhodanates or
rhodanide salts. Preferred are thiocyanic acid salts of Na, K, Mg,
Ca and Al.
Alkanolamine is a generic term for a group of compounds in which
trivalent nitrogen is attached directly to a carbon atom of an
alkyl alcohol. A representative formula is
N[H].sub.c[(CH.sub.2).sub.dCH.sub.2OH].sub.e, where c is 3-e, d is
1 to about 5 and e is 1 to about 3. Examples include, but are not
limited to, are monoethanoalamine, diethanolamine and
triethanolamine.
The thiosulfate salts have the general formula
M.sub.f(S.sub.2O.sub.3).sub.g where M is alkali metal or an
alkaline earth metal or aluminum, and f is 1 or 2 and g is 1, 2 or
3, depending on the valencies of the M metal elements. Preferred
are thiosulfate acid salts of Na, K, Mg, Ca and Al.
The carboxylic acid salts have the general formula RCOOM wherein R
is H or C.sub.1 to about C.sub.10 alkyl, and M is alkali metal or
an alkaline earth metal or aluminum. Preferred are carboxylic acid
salts of Na, K, Mg, Ca and Al. A preferred carboxylic acid salt is
calcium formate.
A preferred polyhydroxylalkylamine has the general formula
##STR00019## wherein h is 1 to 3, i is 1 to 3, j is 1 to 3, and k
is 0 to 3. A preferred polyhydroxyalkylamine is
tetrahydroxyethylethylenediamine.
Set retarding, or also known as delayed-setting or hydration
control, admixtures are used to retard, delay, or slow the rate of
setting of concrete. They can be added to the concrete mix upon
initial batching or sometime after the hydration process has begun.
Set retarders are used to offset the accelerating effect of hot
weather on the setting of concrete, or delay the initial set of
concrete or grout when difficult conditions of placement occur, or
problems of delivery to the job site, or to allow time for special
finishing processes. Most set retarders also act as low level water
reducers and can also be used to entrain some air into concrete.
Lignosulfonates, hydroxylated carboxylic acids, borax, gluconic,
tartaric and other organic acids and their corresponding salts,
phosphonates, certain carbohydrates such as sugars and sugar-acids
and mixtures thereof can be used as retarding admixtures.
The term air entrainer includes any chemical that will entrain air
in cementitious compositions. Air entrainers can also reduce the
surface tension of a composition at low concentration.
Air-entraining admixtures are used to purposely entrain microscopic
air bubbles into concrete. Air-entrainment dramatically improves
the durability of concrete exposed to moisture during cycles of
freezing and thawing. In addition, entrained air greatly improves a
concrete's resistance to surface scaling caused by chemical
deicers. Air entrainment also increases the workability of fresh
concrete while eliminating or reducing segregation and bleeding.
Materials used to achieve these desired effects can be selected
from wood resin, sulfonated lignin, petroleum acids, proteinaceous
material, fatty acids, resinous acids, alkylbenzene sulfonates,
sulfonated hydrocarbons, vinsol resin, anionic surfactants,
cationic surfactants, nonionic surfactants, natural rosin,
synthetic rosin, an inorganic air entrainer, synthetic detergents,
and their corresponding salts, and mixtures thereof. Air entrainers
are added in an amount to yield a desired level of air in a
cementitious composition. Generally, the amount of air entrainers
(about 5% to about 15% solids content) in a cementitious
composition ranges from about 0.07 mL to about 3.9 mL per kilogram
of dry cement. In one embodiment the dosage is about 0.33 mL to
about 0.98 mL per kilogram of dry cement. Weight percentages of the
primary active ingredient of the air entrainers, wherein the
primary active ingredient in the air entrainer provides the desired
effect i.e., entrainment of air in the cementitious composition,
are about 0.001% to about 0.05%; based on the weight of dry
cementitious material. But this can vary widely due to variations
in materials, mix proportion, temperature, and mixing action. An
air entrainer useful with the present admixture composition can be
any known air entrainer for cement, including natural resin,
synthetic resin, and mixtures thereof. Examples of air entrainers
that can be used comprise, but are not limited to MB AE 90, MB VR
and MICRO AIR.RTM., all available from Master Builders Inc. of
Cleveland, Ohio.
Air detrainers are used to decrease the air content in the
cementitious composition. Examples of air detrainers that can be
used comprise, but are not limited to tributyl phosphate, dibutyl
phthalate, octyl alcohol, water-insoluble esters of carbonic and
boric acid, acetylenic diols, ethylene oxide-propylene oxide block
copolymers and silicones.
Corrosion inhibitors in concrete serve to protect embedded
reinforcing steel from corrosion. The high alkaline nature of the
concrete causes a passive and non-corroding protective oxide film
to form on the steel. However, carbonation or the presence of
chloride ions from deicers or seawater, together with oxygen can
destroy or penetrate the film and result in corrosion.
Corrosion-inhibiting admixtures chemically slow this corrosion
reaction. The materials most commonly used to inhibit corrosion are
calcium nitrite, sodium nitrite, sodium benzoate, certain
phosphates or fluorosilicates, fluoroaluminates, amines, organic
based water repelling agents, and related chemicals.
Dampproofing admixtures reduce the permeability of concrete that
has low cement contents, high water-cement ratios, or a deficiency
of fines in the aggregate portion. These admixtures retard moisture
penetration into dry concrete and include certain soaps, stearates,
and petroleum products.
Permeability reducers are used to reduce the rate at which water
under pressure is transmitted through concrete. Silica fume, fly
ash, ground slag, metakaolin, natural pozzolans, water reducers,
and latex can be employed to decrease the permeability of the
concrete.
Pumping aids are added to concrete mixes to improve pumpability.
These admixtures thicken the fluid concrete, i.e., increase its
viscosity, to reduce de-watering of the paste while it is under
pressure from the pump. Among the materials used as pumping aids in
concrete are organic and synthetic polymers, hydroxyethylcellulose
(HEC) or HEC blended with dispersants, organic flocculents, organic
emulsions of paraffin, coal tar, asphalt, acrylics, bentonite and
pyrogenic silicas, natural pozzolans, fly ash and hydrated
lime.
Bacteria and fungal growth on or in hardened concrete may be
partially controlled through the use of fungicidal, germicidal, and
insecticidal admixtures. The most effective materials for these
purposes are polyhalogenated phenols, dialdrin emulsions, and
copper compounds.
Finely divided mineral admixtures are materials in powder or
pulverized form added to concrete before or during the mixing
process to improve or change some of the plastic or hardened
properties of portland cement concrete. The finely divided mineral
admixtures can be classified according to their chemical or
physical properties as: cementitious materials; pozzolans;
pozzolanic and cementitious materials; and nominally inert
materials.
A pozzolan is a siliceous or aluminosiliceous material that
possesses little or no cementitious value but will, in the presence
of water and in finely divided form, chemically react with the
calcium hydroxide produced during the hydration of portland cement
to form materials with cementitious properties. Diatomaceous earth,
opaline cherts, clays, shales, fly ash, silica fume, volcanic tuffs
and pumicites are some of the known pozzolans. Certain ground
granulated blast-furnace slags and high calcium fly ashes possess
both pozzolanic and cementitious properties. Natural pozzolan is a
term of art used to define the pozzolans that occur in nature, such
as volcanic tuffs, pumices, trasses, diatomaceous earths, opaline,
cherts, and some shales. Nominally inert materials can also include
finely divided raw quartz, dolomites, limestones, marble, granite,
and others. Fly ash is defined in ASTM C618.
Alkali-reactivity reducers can reduce the alkali-aggregate reaction
and limit the disruptive expansion forces that this reaction can
produce in hardened concrete. Pozzolans (fly ash, silica fume),
blast-furnace slag, salts of lithium and barium are especially
effective.
Fresh concrete can sometimes be harsh because of faulty mixture
proportions or certain aggregate characteristics such as particle
shape and improper grading. Under these conditions, entrained air,
which acts like a lubricant, can be used as a workability improving
agent. Other workability agents include certain water reducing
admixtures, some viscosity modifying admixtures and certain finely
divided admixtures.
In the construction field, many methods of protecting concrete from
tensile stresses and subsequent cracking have been developed
through the years. One modern method involves distributing fibers
throughout a fresh concrete mixture. Upon hardening, this concrete
is referred to as fiber-reinforced concrete. Fibers can be made of
zirconium materials, carbon, steel, fiberglass, or synthetic
materials, e.g., polypropylene, nylon, polyethylene, polyester,
rayon, high-strength aramid, or mixtures thereof.
The shrinkage reducing agent which can be used comprises but is not
limited to RO(AO).sub.1-10H, wherein R is a C.sub.1-5 alkyl or
C.sub.5-6 cycloalkyl radical and A is a C.sub.2-3 alkylene radical,
alkali metal sulfate, alkaline earth metal sulfates, alkaline earth
oxides, preferably sodium sulfate and calcium oxide.
TETRAGUARD.RTM. is an example of a shrinkage reducing agent
(available from Master Builders Inc. of Cleveland, Ohio) that can
be used.
Aggregate can be included in the cementitious formulation to
provide for mortars which include fine aggregate, and concretes
which also include coarse aggregate. The fine aggregate are
materials that almost entirely pass through a Number 4 sieve (ASTM
C 125 and ASTM C 33), such as silica sand. The coarse aggregate are
materials that are predominantly retained on a Number 4 sieve (ASTM
C 125 and ASTM C 33), such as silica, quartz, crushed round marble,
glass spheres, granite, limestone, calcite, feldspar, alluvial
sands, sands or any other durable aggregate, and mixtures
thereof.
In one embodiment, the cementitious formulation may have a
water-to-cementitious materials ratio of about 0.38 to about
0.65.
Examples of the previously described compositions were tested for
their effect on the color and viscosity of cementitious
compositions.
To compare the pigments dispersing properties of the
polycarboxylate containing liquid coloring suspension with the
liquid coloring suspensions of the prior art several liquid
coloring suspension samples were prepared.
TABLE-US-00001 TABLE 1 Sample 1 Sample 2 Sample 3 water 37.48 37.87
21.96 melamine dispersant 2.66 acrylic dispersant 0.62 PC
dispersant 2.24 2.24 defoamer 0.06 0.06 0.06 dry iron oxide 59.07
59.70 70.00 pigment
Sample 1 which contained a melamine and acrylic dispersant was
unable to disperse the pigments in the solution when the
concentration of pigment solids was about 60%. This is in contrast
to the liquid coloring suspension in which a polycarboxylate
dispersant dispersed a pigment concentration of 60% (sample 2) and
70% (sample 3) in a liquid coloring suspension.
To test for an improvement in color in cementitious compositions
over the prior art, samples of the liquid coloring suspension were
added to cementitious compositions and the tint strength was tested
and compared to the tint strength of cementitious compositions
containing a prior art liquid coloring suspension.
TABLE-US-00002 Mix Design: cement (type I/II) 80 pigment dispersion
2.4 dose/cwt 3 pva 4 water 28 w/c 0.35
The pigment dispersion, pva (polyvinyl acetate), and water were
added to the cement and stirred. Using a 5 millimeter (#50) draw
down rod, a sample of the mixture was drawn down onto a clean
Leneta card and allowed to cure at ambient temperature overnight.
The following day the tinting strength of the liquid coloring
suspension was compared to the tinting strength of the prior art
liquid coloring suspension.
TABLE-US-00003 TABLE 2 Tint prior art Dispersion Strength of liquid
liquid coloring liquid coloring Dose coloring suspension suspension
(%/cwt) suspension (%) Yellow iron oxide Yellow iron oxide 3 111
Light Red iron oxide Yellow iron oxide 3 149
The liquid coloring suspension produced increased color (higher
tint) in a cementitious composition as compared to the prior liquid
coloring suspension (111% and 149% compared to 100%).
To evaluate the performance of the liquid coloring suspension with
different polycarboxylate dispersant chemistries, samples were
prepared that contained the polycarboxylate dispersants and iron
oxide pigment. The samples were tested for the ability of the
polycarboxylate dispersants to disperse the pigment in the liquid
coloring suspension and to color the concrete mixtures. The
concrete mixtures were prepared using 20.9 (lbs/yd3) cement, 68.7
(lbs/yd3) sand, 84.8 (lbs/yd3) stone and 13.9 (lbs/yd3) water. PC
(polycarboxylate) dispersants 1, 2 and 5 comprise the dispersant
structure of formula (j) above and PC dispersants 3 and 4 comprise
the dispersant structure of formula (d) above.
TABLE-US-00004 TABLE 3 Sample Sample Sample Sample Sample 4 5 6 7 8
Water 24.87 24.87 24.87 24.87 24.87 PC dispersant 1 2.24 PC
dispersant 2 2.24 PC dispersant 3 2.24 PC dispersant 4 2.24 PC
dispersant 5 2.24 Defoamer 0.04 0.04 0.04 0.04 0.04 Dry yellow
59.70 59.70 59.70 59.70 59.70 iron oxide pigment Dispersant high
moderately very high moderate mod- efficiency.sup.1 high erate
Dispersion 1880 2060 2240 2310 2300 viscosity Dispersion 2 5 1 3 4
effect on concrete appearance.sup.2 .sup.1qualitative determination
of ease of incorporating the pigment into the dispersion
.sup.2visual determination of appearance; ranking 1-5 with 1 being
the most uniform and least amount of efflorescence
Table 3 demonstrates that all of the polycarboxylate dispersants
dispersed the iron oxide pigment particles in the liquid coloring
suspensions without creating a solution with high viscosity. A
visual determination of appearance of the concrete mixtures showed
that mixtures displayed little efflorescence.
The liquid coloring suspension was tested at varying temperatures
(50.degree., 70.degree., and 90.degree. Fahrenheit) with different
iron oxide pigments to determine if there was a change in liquid
coloring suspension viscosity over time. Table 4 shows the sample
formulations for the liquid coloring suspensions that were tested.
The results of the testing are displayed in FIGS. 1 to 3. The
graphs in FIGS. 1 to 3 show that even at varying temperatures the
viscosity of the liquid coloring suspension does not increase over
time, but rather initially decreases and then stabilizes over
time.
TABLE-US-00005 TABLE 4 Light red Medium red Samples 110 130 Black
Yellow Water 37.48 37.36 32.81 37.86 Caustic soda, 50% 0.40 0.22
0.02 0.26 (w/w) Clay thickener 0.11 0.29 0.40 0.24 Cellulose
thickener 0.11 0.29 PC dispersant 1 3.68 3.57 3.53 3.67 Iron Oxide
Red 110 57.97 Iron Oxide Red 130 58.00 Iron Oxide Black 330 55.34
carbon black dispersion 7.60 Iron Oxide Yellow 313 57.70 Biocide
0.25 0.27 0.30 0.27
It will be understood that the embodiment(s) described herein
is/are merely exemplary, and that one skilled in the art may make
variations and modifications without departing from the spirit and
scope of the invention. All such variations and modifications are
intended to be included within the scope of the invention as
described hereinabove. Further, all embodiments disclosed are not
necessarily in the alternative, as various embodiments of the
invention may be combined to provide the desired result.
* * * * *